CN114436804A - Alkylanthraquinone compositions and methods of making the same - Google Patents
Alkylanthraquinone compositions and methods of making the same Download PDFInfo
- Publication number
- CN114436804A CN114436804A CN202011120963.7A CN202011120963A CN114436804A CN 114436804 A CN114436804 A CN 114436804A CN 202011120963 A CN202011120963 A CN 202011120963A CN 114436804 A CN114436804 A CN 114436804A
- Authority
- CN
- China
- Prior art keywords
- anthracene
- alkyl
- amount
- composition
- anthraquinone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 680
- 238000000034 method Methods 0.000 title claims abstract description 92
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 1421
- -1 alkyl anthraquinone Chemical class 0.000 claims abstract description 627
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 294
- 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 claims abstract description 268
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 238
- 238000000926 separation method Methods 0.000 claims abstract description 224
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 164
- 238000009835 boiling Methods 0.000 claims abstract description 117
- 230000003647 oxidation Effects 0.000 claims abstract description 114
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 102
- 230000029936 alkylation Effects 0.000 claims abstract description 91
- 239000000126 substance Substances 0.000 claims abstract description 76
- 230000008569 process Effects 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004821 distillation Methods 0.000 claims description 265
- 239000002904 solvent Substances 0.000 claims description 152
- 238000006243 chemical reaction Methods 0.000 claims description 134
- 239000000047 product Substances 0.000 claims description 123
- 239000003054 catalyst Substances 0.000 claims description 122
- 239000007810 chemical reaction solvent Substances 0.000 claims description 110
- 239000007795 chemical reaction product Substances 0.000 claims description 75
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 59
- 239000007800 oxidant agent Substances 0.000 claims description 54
- 238000010992 reflux Methods 0.000 claims description 52
- 125000001424 substituent group Chemical group 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 42
- 230000001590 oxidative effect Effects 0.000 claims description 41
- 229940100198 alkylating agent Drugs 0.000 claims description 38
- 239000002168 alkylating agent Substances 0.000 claims description 38
- 238000004519 manufacturing process Methods 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- 150000001875 compounds Chemical class 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 29
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 28
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 28
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 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 24
- 229940045799 anthracyclines and related substance Drugs 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 21
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 18
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 16
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 150000008282 halocarbons Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 10
- 229940076442 9,10-anthraquinone Drugs 0.000 claims description 10
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 10
- 239000011684 sodium molybdate Substances 0.000 claims description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims description 8
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 claims description 8
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 claims description 8
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 8
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 8
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 8
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 claims description 8
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 8
- UZILCZKGXMQEQR-UHFFFAOYSA-N decyl-Benzene Chemical compound CCCCCCCCCCC1=CC=CC=C1 UZILCZKGXMQEQR-UHFFFAOYSA-N 0.000 claims description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 8
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 7
- 230000002152 alkylating effect Effects 0.000 claims description 7
- 238000002955 isolation Methods 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 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 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 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 5
- 229910052750 molybdenum Inorganic materials 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
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- QRFALSDGOMLVIR-UHFFFAOYSA-N 1,2,3,4-tetrabromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1Br QRFALSDGOMLVIR-UHFFFAOYSA-N 0.000 claims description 4
- FEWANSQOXSIFOK-UHFFFAOYSA-N 1,2,3,4-tetraethylbenzene Chemical compound CCC1=CC=C(CC)C(CC)=C1CC FEWANSQOXSIFOK-UHFFFAOYSA-N 0.000 claims description 4
- GMVJKSNPLYBFSO-UHFFFAOYSA-N 1,2,3-tribromobenzene Chemical compound BrC1=CC=CC(Br)=C1Br GMVJKSNPLYBFSO-UHFFFAOYSA-N 0.000 claims description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 4
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 claims description 4
- KKIGDGWHHNXWNM-UHFFFAOYSA-N 1,2,3-tripropylbenzene Chemical compound CCCC1=CC=CC(CCC)=C1CCC KKIGDGWHHNXWNM-UHFFFAOYSA-N 0.000 claims description 4
- NMUWSGQKPAEPBA-UHFFFAOYSA-N 1,2-dibutylbenzene Chemical compound CCCCC1=CC=CC=C1CCCC NMUWSGQKPAEPBA-UHFFFAOYSA-N 0.000 claims description 4
- UUCHLIAGHZJJER-UHFFFAOYSA-N 1,2-diethylnaphthalene Chemical compound C1=CC=CC2=C(CC)C(CC)=CC=C21 UUCHLIAGHZJJER-UHFFFAOYSA-N 0.000 claims description 4
- FQYVVSNFPLKMNU-UHFFFAOYSA-N 1,2-dipentylbenzene Chemical compound CCCCCC1=CC=CC=C1CCCCC FQYVVSNFPLKMNU-UHFFFAOYSA-N 0.000 claims description 4
- VPHBYBUYWBZLEX-UHFFFAOYSA-N 1,2-dipropylbenzene Chemical compound CCCC1=CC=CC=C1CCC VPHBYBUYWBZLEX-UHFFFAOYSA-N 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 4
- LBNXAWYDQUGHGX-UHFFFAOYSA-N 1-Phenylheptane Chemical compound CCCCCCCC1=CC=CC=C1 LBNXAWYDQUGHGX-UHFFFAOYSA-N 0.000 claims description 4
- URGSMJLDEFDWNX-UHFFFAOYSA-N 1-butylnaphthalene Chemical compound C1=CC=C2C(CCCC)=CC=CC2=C1 URGSMJLDEFDWNX-UHFFFAOYSA-N 0.000 claims description 4
- INUWBHWKAMVTNU-UHFFFAOYSA-N 1-ethyl-2-methylnaphthalene Chemical compound C1=CC=C2C(CC)=C(C)C=CC2=C1 INUWBHWKAMVTNU-UHFFFAOYSA-N 0.000 claims description 4
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 claims description 4
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 claims description 4
- HMAMGXMFMCAOPV-UHFFFAOYSA-N 1-propylnaphthalene Chemical compound C1=CC=C2C(CCC)=CC=CC2=C1 HMAMGXMFMCAOPV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 4
- 125000005916 2-methylpentyl group Chemical group 0.000 claims description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000005917 3-methylpentyl group Chemical group 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- NPAXBRSUVYCZGM-UHFFFAOYSA-N carbonic acid;propane-1,2-diol Chemical compound OC(O)=O.CC(O)CO NPAXBRSUVYCZGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- JWJVZCNJVZZHMP-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1.CC(C)(C)C1=CC=CC=C1 JWJVZCNJVZZHMP-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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Classifications
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an alkyl anthraquinone composition and a preparation method thereof. The alkyl anthraquinone composition contains alkyl substituent of anthraquinone, and the molecular formula of the alkyl substituent of anthraquinone is C14+nH8+2nO2N is more than or equal to 2 and less than or equal to 6; the position of the alkyl substituent is alpha and/or beta to the anthraquinone ring. Compared with the traditional single anthraquinone, the alkyl anthraquinone composition provided by the invention has more excellent solubility and chemical properties, and is a novel efficient mixed carrier for preparing hydrogen peroxide. The preparation method provided by the invention is clean and efficient, has strong flexibility, and can meet the product requirements of different mixed alkyl anthraquinones. The alkyl anthraquinone composition is preferably prepared by a combined process of alkylation, separation and oxidation of anthracene, and the alkyl anthracene composition with a specific structure and composition is prepared by alkylation reaction and separation process and then oxidized to prepare the alkyl anthraquinone compositionPrepare the alkylanthraquinone composition. The separation process can obviously reduce the separation difficulty of high boiling point and high condensation point substances and improve the separation yield.
Description
Technical Field
The invention relates to an organic matter composition and a preparation method thereof, in particular to an alkyl anthraquinone composition and a method for preparing the alkyl anthraquinone composition through anthracene.
Background
The prior production process is a phthalic anhydride method, although the process is mature, the process has serious pollution problems, produces a large amount of waste aluminum trichloride, waste sulfuric acid and waste water as byproducts, has high energy and material consumption, and cannot meet the requirements of the current green chemical industry. Therefore, the technology for preparing alkylanthraquinones is in need of renewal.
In addition, as the demand for hydrogen peroxide has increased dramatically, higher demands have also been placed on anthraquinone carriers. It has become common knowledge to improve the hydrogen peroxide productivity by optimizing the solubility properties and chemical stability of alkylanthraquinones. The complex anthraquinone (mixed anthraquinone) has higher solubility than the single anthraquinone. Anthraquinone products with higher solubility and hydrogenation stability can be developed by designing and optimizing the structure of the anthraquinone products. The novel efficient compound type alkyl anthraquinone product has great development potential, but related product design and preparation technologies are not widely reported.
US4404140, US5354937, US4305879 and CN107746372 disclose processes for preparing single type alkylanthraquinone products, respectively.
JP2010105942 discloses a method for preparing mixed anthraquinone by phthalic anhydride method, but the product still takes amylanthraquinone as main material. In the reaction, the pentyl group is decomposed and isomerized to anthraquinone and ethyl/butyl anthraquinone with low carbon number. Wherein the amylanthraquinone content is 98.2-99.1 wt%, and the other less than 3 wt% comprises anthraquinone, ethylanthraquinone and butylanthraquinone.
US6399795 and US 2002/0035280 disclose an optimized process for the preparation of 2-hexylanthraquinone by the naphthoquinone process, which improves the space-time yield and product purity, in particular the conversion in the oxidation reaction process. The oxidation temperature is 50-150 ℃, and the pressure is 1-10 bar; the catalyst is a combination of inorganic base NaOH and organic amine, and the molar ratio of the inorganic base NaOH to the organic amine is 1:1-3: 1; the oxidation solvent is a combination of polar/nonpolar solvents, and the mass ratio of the two solvents is 1:2-1: 4.
CN107602368A discloses a method for preparing 2-amylanthraquinone by an anthracene alkylation-oxidation method, comprising the first step of preparing 2-amylanthracene by performing alkylation reaction on anthracene and isoamylene, wherein a catalyst is an Mg-MWW molecular sieve; secondly, the 2-pentylanthracene is oxidized to prepare the 2-pentylanthraquinone, the oxidant is oxygen, and the catalyst is gamma-Al2O3The solid catalyst prepared from Mn, Mg, Fe and the like is loaded, and the experimental result shows that the highest oxidation reaction yield of the 2-amylanthraquinone is 28.4 percent.
As can be seen, at present, no composite alkyl anthraquinone product and feasible preparation technology report exists.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, provides an alkylanthraquinone composition which is a core raw material for preparing hydrogen peroxide, and further provides a preparation method of the alkylanthraquinone composition.
Compared with a single anthraquinone product, the solubility and chemical stability of the alkyl anthraquinone composition provided by the invention are remarkably improved, and the product types of 'carrier' anthraquinone are enriched. The preparation method of the alkylanthraquinone composition provided by the invention is simple, efficient, environment-friendly and flexible, and can meet the requirements of different product specifications.
In order to achieve the above objects, according to one aspect of the present invention, there is provided an alkylanthraquinone composition, wherein the alkylanthraquinone composition comprises an alkyl substituent of anthraquinone of the formula C14+nH8+2nO2，2≤n≤6; the position of the alkyl substituent is alpha and/or beta to the anthraquinone ring.
Preferably, the alkyl substituent of the anthraquinone is represented by structural formula (1):
any three substituents are H, and the rest substituents are alkyl with the carbon atom number of 2-6; or,
any two substituents are H, the other two substituents are each independently an alkyl group having 2 to 4 carbon atoms, and the total number of carbon atoms is 6 or less.
Preferably, the alkylanthraquinone composition contains C16H12O2、C17H14O2、C18H16O2、C19H18O2And C20H20O2At least any two of the substances in (1).
In a second aspect, the present invention provides a process for the preparation of the alkylanthraquinone composition, wherein the process comprises: contacting the alkyl anthracene composition with an oxidizing agent under oxidizing conditions and in the presence of an oxidizing reaction solvent and an oxidizing catalyst to effect an oxidation reaction to produce an alkyl anthracene oxidation product comprising an alkyl anthraquinone composition having an alkyl substituent of anthraquinone of formula C14+nH8+2nO2N is more than or equal to 2 and less than or equal to 6; the position of the alkyl substituent is alpha position and/or beta position of the anthraquinone ring;
wherein the alkyl anthracene composition contains an alkyl substituent of anthracene, and the molecular formula of the alkyl substituent of the anthracene is C14+ nH10+2nN is more than or equal to 2 and less than or equal to 6; the position of the alkyl substituent is alpha and/or beta to the anthracycline.
Preferably, the alkyl anthracene composition is contacted with the oxidizing agent in a manner that: and (3) separating the alkyl anthracene composition from the anthracene alkylation reaction product, and contacting the mixture of the separated alkyl anthracene composition, the oxidation catalyst and the oxidation reaction solvent with an oxidant for oxidation reaction to obtain the alkyl anthraquinone composition.
Preferably, the alkyl anthracene composition is contacted with the oxidizing agent in a manner that: contacting a mixture of an anthracene alkylation reaction product containing the alkyl anthracene composition, an oxidation catalyst, and optionally an oxidation reaction solvent, with an oxidizing agent for oxidation to produce an alkyl anthracene oxidation product containing the alkyl anthraquinone composition, and separating the alkyl anthraquinone composition from the alkyl anthracene oxidation product.
Preferably:
mode 1C: the alkylation reaction solvent used in the anthracene alkylation reaction is the same as the oxidation reaction solvent used in the alkyl anthracene oxidation reaction, the alkylation catalyst in the anthracene alkylation reaction product is separated to obtain an alkylation product mixture containing a light component with a boiling point lower than that of anthracene, selectively contained anthracene and an alkyl anthracene system, wherein the alkyl anthracene system contains the alkyl anthracene composition, and the mixture of the alkylation product mixture and the oxidation catalyst is contacted with an oxidizing agent for oxidation reaction to obtain an alkyl anthracene oxidation product containing the alkyl anthraquinone composition; or,
mode 2C: the alkylation reaction solvent used in the anthracene alkylation reaction is different from the oxidation reaction solvent used in the alkyl anthracene oxidation reaction, the alkylation catalyst and the alkylation reaction solvent in the anthracene alkylation reaction product are separated, so that an alkylation product mixture containing anthracene and an alkyl anthracene system with a boiling point lower than that of anthracene is obtained, the anthracene selectively contained in the anthracene and the alkyl anthracene system contains the alkyl anthracene composition, and the mixture of the alkylation product mixture, the oxidation catalyst and the oxidation reaction solvent is contacted with an oxidizing agent for oxidation reaction to obtain an alkyl anthracene oxidation product containing the alkyl anthraquinone composition.
Compared with single anthraquinone, the alkylanthraquinone composition provided by the invention has higher solubility and chemical stability, is an excellent composite carrier for preparing hydrogen peroxide, and is expected to become the future development direction of the industry.
The preparation method of the alkylanthraquinone composition provided by the invention can realize the preparation of alkylanthraquinone compositions with different compositions and different structures by regulating and matching the reaction-separation process, has strong process flexibility and wide adaptability, and can meet the product requirements of different specifications.
In the preparation method of the alkyl anthraquinone composition, the separation method of the anthracene and the alkyl anthracene system in the process route of preparing the anthracene alkylation reaction product through anthracene alkylation, separating the anthracene and the alkyl anthracene system, separating the alkyl anthracene composition, oxidizing and obtaining the alkyl anthraquinone composition product, or the separation method of the anthraquinone and the alkyl anthraquinone mixture in the process route of preparing the anthracene alkylation reaction product through anthracene alkylation, oxidizing and separating the anthraquinone and the alkyl anthraquinone composition to obtain the alkyl anthraquinone composition product is provided, and a special auxiliary distillation technology is developed by introducing a distillation solvent in the traditional distillation process, so that the separation efficiency of the anthracene or the anthraquinone can be obviously improved, the difficulty in the separation process of the anthracene or the anthraquinone is greatly reduced, and the overall separation efficiency is improved.
The preparation method of the alkylanthraquinone composition provided by the invention is simple and efficient, the separation and recovery difficulty of the oxidation catalyst is low, no corrosivity exists, and the equipment investment and the post-treatment cost of the oxidation waste liquid are reduced.
The invention prepares the alkyl anthraquinone system containing the alkyl anthraquinone composition by regulating and controlling the reaction and controlling the composition characteristics, controls the purity of the product by matching and separating, and realizes the directional preparation of the alkyl anthraquinone composition by the effective coupling of the process.
In addition, the preparation method of the alkylanthraquinone composition provided by the invention also has the advantages of simple process, high efficiency and small pollution.
Drawings
FIG. 1 is a specific embodiment of the present invention providing an alkylanthraquinone composition C from anthracene14+nH8+2nO2(2. ltoreq. n. ltoreq.6);
FIG. 2 is a specific embodiment of the present invention providing an alkylanthraquinone composition C from anthracene14+nH8+2nO2(2. ltoreq. n. ltoreq.6);
FIG. 3 is a flow diagram of a process for distilling a solvent-assisted separation of anthracene according to one embodiment of the invention;
FIG. 4 is a flow chart of a process for distillation solvent assisted separation of anthraquinones in accordance with one embodiment of the present invention.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to the invention, the said alkylanthraquinone composition contains an alkyl substituent of anthraquinone of formula C14+nH8+2nO2N is more than or equal to 2 and less than or equal to 6. Each of the alkylanthraquinone compounds may have the formula C14+nH8+ 2nO2(2. ltoreq. n.ltoreq.6), specifically, the total number of carbons in the alkyl substituent is 2. ltoreq. n.ltoreq.6.
According to the present invention, the structure of each of the materials in the alkylanthraquinone composition is made up of a parent nucleus, 9, 10-anthraquinone ring, with alkyl substitution. The position of the alkyl substituent is in the alpha and/or beta position, preferably in the beta position, of the anthraquinone ring.
According to a preferred embodiment of the present invention, the alkyl substituent of the anthraquinone is represented by the structural formula (1):
any three substituents are H, and the rest substituents are alkyl with the carbon atom number of 2-6; or,
any two substituents are H, the other two substituents are each independently an alkyl group having 2 to 4 carbon atoms, and the total number of carbon atoms is 6 or less.
According to the invention, the alkylanthraquinone composition preferably contains C16H12O2、C17H14O2、C18H16O2、C19H18O2And C20H20O2Wherein any two species refer to any two species of different molecular formula. The substance having the same formula includes a plurality of isomers including a difference in the number of substituents, a difference in the structure of the substituents and a difference in the position of the substituents, and each formula includes the sum of all isomers having such a formula.
According to the present invention, the alkylanthraquinone composition of the first embodiment, alkylanthraquinone composition (I), is based on the total weight of said alkylanthraquinone composition, C16H12O2In an amount of 10-96 wt.%, C17H14O2In an amount of 0-10 wt.%, C18H16O2In an amount of 3.5 to 89.5 wt.%, C19H18O2In an amount of 0-30 wt.%, C20H20O2In an amount of 0.5 to 50 wt%; preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 30-80 wt.%, C17H14O2In an amount of 0-5 wt.%, C18H16O2In an amount of 15-65 wt.%, C19H18O2In an amount of 0-15 wt.%, C20H20O2In an amount of 5 to 30% by weight; most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 35-55 wt.%, C17H14O2In an amount of 0-2 wt.%, C18H16O2In an amount of 25-50 wt.%, C19H18O2In an amount of 0-10 wt.%, C20H20O2Is contained in an amount of 10 to 25 wt%.
According to the present invention, the alkylanthraquinone composition of the second embodiment, alkylanthraquinone composition (II), is based on the total weight of said alkylanthraquinone composition, C16H12O2In an amount of 0 to 10 weight partsAmount% C17H14O2In an amount of 10 to 96.5 wt.%, C18H16O2In an amount of 0-30 wt.%, C19H18O2In an amount of 0-30 wt.%, C20H20O2The content of (B) is 3.5-90 wt%; preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-5 wt.%, C17H14O2In an amount of 30-80 wt.%, C18H16O2In an amount of 0-15 wt.%, C19H18O2In an amount of 0-15 wt.%, C20H20O2The content of (A) is 15-70 wt%; most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-2 wt.%, C17H14O2In an amount of 40-70 wt.%, C18H16O2In an amount of 0-15 wt.%, C19H18O2In an amount of 0-5 wt.%, C20H20O2Is contained in an amount of 15 to 45% by weight.
According to the present invention, based on the structural and compositional features, the alkylanthraquinone composition of the third embodiment, alkylanthraquinone composition (III), based on the total weight of said alkylanthraquinone composition, C16H12O2In an amount of 0-10 wt.%, C17H14O2In an amount of 0-10 wt.%, C18H16O2In an amount of 10 to 99.1 wt.%, C19H18O2In an amount of 0.45-50 wt.%, C20H20O2The content of (B) is 0.45-30 wt%; preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-5 wt.%, C17H14O2In an amount of 0-5 wt.%, C18H16O2In an amount of 40-95 wt.%, C19H18O2In an amount of 1-40 wt.%, C20H20O2In an amount of 1 to 25% by weight; most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-2.5 wt.%, C17H14O2In an amount of 0-2.5 wt.%, C18H16O2In an amount of 70 to 90 wt.%, C19H18O2In an amount of 1-10 wt.%, C20H20O2Is contained in an amount of 1 to 15 wt%.
In accordance with the present invention, a fourth embodiment of the alkylanthraquinone composition, alkylanthraquinone composition (IV), based on structural and compositional features, C16H12O2In an amount of 0-10 wt.%, C17H14O2In an amount of 0-10 wt.%, C18H16O2In an amount of 0.5-50 wt.%, C19H18O2In an amount of 10 to 99 wt.%, C20H20O2The content of (B) is 0.5-30 wt%; preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-5 wt.%, C17H14O2In an amount of 0-5 wt.%, C18H16O2In an amount of 1-40 wt.%, C19H18O2In an amount of 40-90 wt.%, C20H20O2In an amount of 1 to 20% by weight; most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-2 wt.%, C17H14O2In an amount of 0-2 wt.%, C18H16O2In an amount of 1-40 wt.%, C19H18O2In an amount of 40-90 wt.%, C20H20O2Is contained in an amount of 1 to 20% by weight.
According to the present invention, the alkylanthraquinone composition (V), which is the alkylanthraquinone composition of the fifth embodiment, is based on the structural and compositional features, andbased on the total weight of the alkylanthraquinone composition, C16H12O2In an amount of 0-10 wt.%, C17H14O2In an amount of 0-10 wt.%, C18H16O2In an amount of 0.5-50 wt.%, C19H18O2In an amount of 0.5-30 wt.%, C20H20O2In an amount of 10 to 99% by weight; preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-5 wt.%, C17H14O2In an amount of 0-5 wt.%, C18H16O2In an amount of 1-40 wt.%, C19H18O2In an amount of 1-30 wt.%, C20H20O2In an amount of 40-95 wt.%; most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-2 wt.%, C17H14O2In an amount of 0-2 wt.%, C18H16O2In an amount of 15-40 wt.%, C19H18O2In an amount of 1-12 wt.%, C20H20O2Is present in an amount of 45 to 75 wt.%.
According to the present invention, it is preferable that,
C16H12O2is a 9, 10-anthraquinone mother nucleus connected with 1 ethyl;
C17H14O2is that 9, 10-anthraquinone mother nucleus is connected with 1 propyl;
C18H16O2the 9, 10-anthraquinone mother nucleus is connected with 1 butyl or 2 ethyl;
C19H18O2is 9, 10-anthraquinone mother nucleus linked to 1 pentyl group, or to 1 ethyl group and 1 propyl group;
C20H20O2is 9, 10-anthraquinone core linked to 1 hexyl group, or to 1 ethyl group and 1 butyl group, or to 2 propyl groups.
According to the invention, the alkyl substituent in the alkyl substituent of the anthraquinone may be selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, tert-pentyl, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 2-dimethylbutyl, 3-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-ethylbutyl, 1-ethylbutyl, 1, 1-dimethyl-2-methylpropyl, 1-methyl-2, 2-dimethylpropyl, 1-methyl-1-ethylpropyl, 1-ethyl-2-methylpropyl. Preferably, the alkyl substituents are selected from one or more of ethyl, isopropyl, 1-methylpropyl, tert-butyl, 1-methylbutyl, tert-pentyl, 1-ethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1-ethylbutyl, 1-dimethyl-2-methylpropyl, 1-methyl-2, 2-dimethylpropyl, 1-methyl-1-ethylpropyl and 1-ethyl-2-methylpropyl.
According to the present invention, it is preferred that the alkyl substituent having 2 to 3 carbon atoms is positioned at the α -position and/or β -position of the 9, 10-anthraquinone core, and further preferably at the β -position of the 9, 10-anthraquinone core; the position of the alkyl substituent containing 4 to 6 carbon atoms is preferably in the beta position of the 9, 10-anthraquinone parent nucleus.
According to the invention, the presence of small amounts of anthraquinone impurities in the alkylanthraquinone composition is allowed without affecting the properties and subsequent purification and use of the alkylanthraquinone composition. Wherein, the composition C is prepared from anthraquinone and alkyl anthraquinone14+nH8+2nO2(2. ltoreq. n. ltoreq.6) based on the total weight of the composition C14+nH8+2nO2The content of (2. ltoreq. n.ltoreq.6) is not less than 90% by weight, more preferably not less than 95% by weight, still more preferably not less than 98% by weight.
According to the present invention, the process for the preparation of the alkylanthraquinone compositions according to the invention, in particular of the alkylanthraquinone compositions (I) to (V) according to the embodiments of the invention, comprises:
(1) reacting anthracene with an alkylating agent to produce the alkyl anthracene composition: contacting anthracene with an alkylating agent under alkylation conditions and in the presence of an alkylation reaction solvent and an alkylation catalyst to carry out alkylation reaction to obtain an anthracene alkylation reaction product containing an alkyl anthracene system, wherein the alkyl anthracene system contains an alkyl anthracene composition containing an alkyl substituent of anthracene, and the molecular formula of the alkyl substituent of anthracene is C14+nH10+2nN is more than or equal to 2 and less than or equal to 6; the position of the alkyl substituent is in the alpha and/or beta position of the anthracycline, preferably in the beta position;
(2) reacting an alkyl anthracene composition with an oxidizing agent to produce the alkyl anthraquinone composition: under the oxidation condition and in the presence of an oxidation reaction solvent and an oxidation catalyst, contacting the alkyl anthracene composition with an oxidant for oxidation reaction to obtain an alkyl anthracene oxidation product containing an alkyl anthraquinone composition, wherein the alkyl anthraquinone composition contains an alkyl substituent of anthraquinone, and the molecular formula of the alkyl substituent of anthraquinone is C14+nH8+2nO2N is more than or equal to 2 and less than or equal to 6; the position of the alkyl substituent is in the alpha and/or beta position, preferably in the beta position, of the anthraquinone ring.
According to the invention, the alkyl anthracene composition is contacted with an oxidant for oxidation reaction to prepare an alkyl anthraquinone composition C14+nH8+2nO2The mode of 2. ltoreq. n.ltoreq.6 can be achieved by the mode A (the raw material for the mode A is the alkyl anthracene composition obtained by separation): contacting anthracene with an alkylating agent for alkylation reaction to obtain an anthracene alkylation reaction product containing an alkyl anthracene system, separating the alkyl anthracene system from the anthracene alkylation reaction product, and separating the alkyl anthracene system from the alkyl anthracene system to prepare the alkyl anthracene composition C14+nH10+2n(2. ltoreq. n.ltoreq.6), oxidizing the separated alkyl anthracene composition to prepare an alkyl anthraquinone composition C14+nH8+2nO2(2. ltoreq. n.ltoreq.6), preferably, the mixture of the separated alkylanthracene composition, the oxidation catalyst and the oxidation reaction solvent is brought into contact with an oxidizing agent to carry out an oxidation reaction to obtain the alkylanthraquinone composition C14+nH8+2nO2(2≤n≤6)。
According to the invention, the alkyl anthracene composition is contacted with an oxidant for oxidation reaction to prepare an alkyl anthraquinone composition C14+nH8+2nO2And n is 2. ltoreq. n.ltoreq.6 can be achieved by mode B (the starting material for mode B is the anthracene alkylation reaction product containing the alkyl anthracene composition): contacting anthracene with an alkylating agent for alkylation reaction to obtain an anthracene alkylation reaction product containing an alkyl anthracene system, wherein the alkyl anthracene system contains the alkyl anthracene composition, when an alkylation reaction solvent used for the anthracene alkylation reaction is different from an oxidation reaction solvent used for the alkyl anthracene oxidation reaction, the alkylation catalyst and the alkylation reaction solvent in the anthracene alkylation reaction product need to be separated to obtain an alkylation product mixture containing a light component with a boiling point lower than that of anthracene, optionally contained anthracene and an alkyl anthracene system, the alkyl anthracene system contains the alkyl anthracene composition, contacting the alkylation product mixture obtained after the alkylation catalyst and the alkylation reaction solvent are separated, the mixture of the oxidation catalyst and the oxidation reaction solvent with an oxidizing agent for oxidation reaction to obtain an alkyl anthracene oxidation product containing the alkyl anthraquinone composition, separating out the alkylanthraquinone composition C14+nH8+2nO2(n is more than or equal to 2 and less than or equal to 6). When the alkylation reaction solvent used in the anthracene alkylation reaction is the same as the oxidation reaction solvent used in the alkyl anthracene oxidation reaction, the alkylation catalyst in the anthracene alkylation reaction product is separated to obtain an alkylation product mixture containing a light component with a boiling point lower than that of anthracene, selectively contained anthracene and an alkyl anthracene system, the mixture obtained by directly mixing the alkylation catalyst and the alkylation catalyst is contacted with an oxidant to carry out oxidation reaction to obtain an alkyl anthracene oxidation product containing the alkyl anthraquinone composition, and then the alkyl anthraquinone composition C is separated14+nH8+2nO2(n is more than or equal to 2 and less than or equal to 6), thereby omitting the step of distillation and replacement of the reaction solvent.
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 an alkyl anthracene composition by alkylation of anthracene. Preferably, for more complete reaction, the contacting is carried out in the following manner: the raw material liquid containing anthracene, alkylation catalyst and alkylation reaction solvent is contacted with alkylation reagent to make alkylation reaction.
According to the present invention, the alkylation reaction is carried out by contacting the raw material solution containing anthracene, an alkylation catalyst and an alkylation reaction solvent with an alkylation reagent, and the raw material solution may be any well-mixed reactor, for example, a tank reactor and a tubular reactor, and may specifically be one or more selected from a stirred tank, a fixed bed, a moving bed, a fluidized bed, a supergravity reactor, a micro-scale reactor and a membrane reactor.
The apparatus and process for the anthraalkylation reaction according to the present invention may be carried out in a manner conventional in the art.
According to the present invention, the alkylating agent may be any alkylating agent that is conventional in the art, as long as the total carbon number of the alkyl substituent is satisfied to meet the requirements of the present invention, and for example, the alkylating agent may be one or more of alkylating agents containing 2 to 6 carbon atoms; preferably, the alkylating agent is one or more of olefin, alcohol, halogenated hydrocarbon and ether substances containing 2-6 carbon atoms; more preferred are monoolefins having 2 to 6 carbon atoms, monohydric alcohols and monohydric halogenated hydrocarbons, and still more preferred are monoolefins having 2 to 6 carbon atoms.
According to the invention, the amount of alkylating agent used in the course of the anthracene alkylation reaction is such that the introduction of alkyl groups into the anthracene nucleus to produce alkyl anthracene is achieved, preferably with a molar ratio of anthracene to alkylating agent of from 0.05:1 to 20:1, preferably from 0.1:1 to 5: 1.
According to the invention, in the process of anthracene alkylation reaction, the alkylation reaction solvent is an inert organic solvent capable of dissolving anthracene. Specifically, the alkylation reaction solvent is a solvent with a dielectric constant of 1-10 at 20 ℃, and the alkylation reaction solvent is C6And above, preferably C6-C12One 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 the poly-substituents of benzene,the substituent being C1-C4One or more of alkyl and halogen elements of (a); further preferably, the alkylation reaction solvent is one or more of polyalkyl substitutes of benzene; most preferably, the alkylation reaction solvent is selected from one or more of 1,2, 3-trimethylbenzene, 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene and 1,2,3, 4-tetramethylbenzene. The amount of the alkylation reaction solvent is only required to ensure that the anthracene can be sufficiently 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, the manner of contacting anthracene with the alkylating agent under alkylation conditions and in the presence of the alkylation solvent and the catalyst during the anthracene alkylation reaction is not particularly limited, and preferably, in order to ensure better progress of the alkylation reaction, the contacting manner is: the raw material liquid containing anthracene, alkylation catalyst and alkylation reaction solvent is contacted with alkylation reagent to make alkylation reaction. Specifically, anthracene, a catalyst and an alkylation reaction solvent are prepared into a raw material solution of anthracene-alkylation catalyst-alkylation reaction solvent, and then an alkylation reagent is added for alkylation reaction. Preferably, the feed solution of the anthracene-alkylation catalyst-alkylation reaction solvent is formulated at a temperature of 80 to 250 deg.C, more preferably 90 to 200 deg.C.
In accordance with the present invention, the alkylation reaction conditions during the anthracene alkylation reaction generally include: the reaction temperature can be 80-250 ℃, preferably 90-200 ℃; the reaction pressure may be 0-2MPa, preferably 0-1 MPa; the reaction time may be from 0.01 to 48 hours, preferably from 0.5 to 24 hours.
According to the invention, in the course of the anthracene alkylation reaction, the alkylation reaction is carried out in the presence of an alkylation catalyst in order to make the alkylation reaction easier to carry out. Specifically, the alkylation catalyst may be any form and kind of catalyst capable of catalyzing the alkylation of anthracene, including but not limited to: one or more of kaolin, bentonite, montmorillonite, zeolite, an X molecular sieve, a Y molecular sieve, a beta molecular sieve, MCM-41, SBA-15, cation exchange resin, perfluorinated sulfonic acid resin, immobilized sulfuric acid, immobilized sulfonic acid, immobilized phosphoric acid, silicon-aluminum composite oxide, sulfuric acid, perchloric acid, tetrafluoroboric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, boron trifluoride, aluminum trichloride and zinc dichloride; further preferably selected from one or more of zeolite, Y molecular sieve, MCM-41, SBA-15, perfluorosulfonic acid resin, immobilized sulfonic acid, silicon-aluminum composite oxide, sulfuric acid, tetrafluoroboric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid. The amount of alkylation catalyst may also be used in an amount of 0.01 to 50 wt%, preferably 0.5 to 30 wt%, more preferably 1 to 20 wt%, based on the total weight of the feed solution containing anthracene, alkylation reaction solvent, and alkylation catalyst, in accordance with conventional amounts in the art.
According to the invention, to obtain the alkylanthraquinone compositions of the invention, in particular alkylanthraquinone compositions (I) to (V), by means of mode A, it is necessary to first prepare an alkylanthraquinone composition C14+nH10+2n(2. ltoreq. n.ltoreq.6), in particular alkyl anthracene compositions (I) to (V). The raw material for preparing the alkyl anthraquinone composition by oxidation, namely the alkyl anthracene composition, comprises a plurality of alkyl substitutes of anthracene, and the molecular formula of the alkyl substitutes of the anthracene can be uniformly described as C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The molecular formula of each of the alkyl anthracene compositions may be C14+nH10+2n(2. ltoreq. n.ltoreq.6). Specifically, the alkyl anthracene composition contains an alkyl substituent of anthracene, which is represented by structural formula (2):
any three substituents are H, and the rest substituents are alkyl with the carbon atom number of 2-6; or,
any two substituents are H, the other two substituents are each independently alkyl with 2-4 carbon atoms, and the sum of the carbon atoms is less than or equal to 6.
According to the present invention, preferably, the alkyl anthracene composition contains C16H14、C17H16、C18H18、C19H20And C20H22Wherein any two species refer to any two species of different molecular formula. The substance having the same formula includes various isomers including a difference in the number of substituents, a difference in the structure of the substituents and a difference in the position of the substituents, and each formula represents the sum of all isomers having such a formula.
According to the present invention, specifically, an anthracene is contacted with an alkylating agent containing 2 carbon atoms to carry out an alkylation reaction, and the obtained anthracene alkylation reaction product contains an alkyl anthracene composition (I), wherein C is the total weight of the alkyl anthracene composition16H14In an amount of 10-95 wt.%, C17H16In an amount of 0-10 wt.%, C18H18In an amount of 4-89 wt.%, C19H20In an amount of 0-30 wt.%, C20H22In an amount of 1 to 50% by weight; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 30-80 wt.%, C17H16In an amount of 0-5 wt.%, C18H18In an amount of 15-65 wt.%, C19H20In an amount of 0-15 wt.%, C20H22In an amount of 5 to 30% by weight; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 35-55 wt.%, C17H16In an amount of 0-2 wt.%, C18H18In an amount of 25-50 wt.%, C19H20In an amount of 0-10 wt.%, C20H22Is contained in an amount of 10 to 25 wt%.
Specifically, anthracene is contacted with an alkylating agent containing 3 carbon atoms for alkylation reaction, and an anthracene alkylation reaction product contains an alkyl anthracene composition (II),wherein, based on the total weight of the alkyl anthracene composition, C16H14In an amount of 0-10 wt.%, C17H16In an amount of 10-96 wt.%, C18H18In an amount of 0-30 wt.%, C19H20In an amount of 0-30 wt.%, C20H22The content of (B) is 4-90 wt%; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-5 wt.%, C17H16In an amount of 30-80 wt.%, C18H18In an amount of 0-15 wt.%, C19H20In an amount of 0-15 wt.%, C20H22The content of (A) is 15-70 wt%; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-2 wt.%, C17H16In an amount of 40-70 wt.%, C18H18In an amount of 0-15 wt.%, C19H20In an amount of 0-5 wt.%, C20H22Is contained in an amount of 15 to 45% by weight.
Specifically, the anthracene is contacted with an alkylating agent containing 4 carbon atoms for alkylation reaction to obtain an anthracene alkylation reaction product containing an alkyl anthracene composition (III), wherein C is the total weight of the alkyl anthracene composition16H14In an amount of 0-10 wt.%, C17H16In an amount of 0-10 wt.%, C18H18In an amount of 10 to 99 wt.%, C19H20In an amount of 0.5-50 wt.%, C20H22The content of (B) is 0.5-30 wt%; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-5 wt.%, C17H16In an amount of 0-5 wt.%, C18H18In an amount of 40-95 wt.%, C19H20In an amount of 1-40 wt.%, C20H22In an amount of 1 to 25% by weight; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-2.5 wt.%, C17H16The content of (B) is 0-2.5 weightAmount% C18H18In an amount of 70 to 90 wt.%, C19H20In an amount of 1-10 wt.%, C20H22Is contained in an amount of 1 to 15% by weight.
Specifically, the anthracene is contacted with an alkylating agent containing 5 carbon atoms for alkylation reaction, and the obtained anthracene alkylation reaction product contains an alkyl anthracene composition (IV), wherein C is the total weight of the alkyl anthracene composition16H14In an amount of 0-10 wt.%, C17H16In an amount of 0-10 wt.%, C18H18In an amount of 0.5-50 wt.%, C19H20In an amount of 10 to 99 wt.%, C20H22The content of (B) is 0.5-30 wt%; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-5 wt.%, C17H16In an amount of 0-5 wt.%, C18H18In an amount of 1-40 wt.%, C19H20In an amount of 40-90 wt.%, C20H22In an amount of 1 to 20% by weight; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-2 wt.%, C17H16In an amount of 0-2 wt.%, C18H18In an amount of 1-40 wt.%, C19H20In an amount of 40-90 wt.%, C20H22Is contained in an amount of 1 to 20% by weight.
Specifically, the anthracene is contacted with an alkylating agent containing 6 carbon atoms for alkylation reaction, and the obtained anthracene alkylation reaction product contains an alkyl anthracene composition (V), wherein C is the total weight of the alkyl anthracene composition16H14In an amount of 0-10 wt.%, C17H16In an amount of 0-10 wt.%, C18H18In an amount of 0.5-50 wt.%, C19H20In an amount of 0.5-30 wt.%, C20H22In an amount of 10 to 99% by weight; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-5 wt.%, C17H16In an amount of 0-5 wt.%, C18H18In an amount of 1-40 wt.%, C19H20In an amount of 1-30 wt.%, C20H22In an amount of 40-95 wt.%; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-2 wt.%, C17H16In an amount of 0-2 wt.%, C18H18In an amount of 15-40 wt.%, C19H20In an amount of 1-12 wt.%, C20H22Is present in an amount of 45 to 75 wt.%.
The alkylating reagent forms carbonium ions under the action of a catalyst, and the carbonium ions are easy to generate secondary reaction to generate a plurality of carbonium ions with different structures and the same carbon number or different carbon numbers; different carbonium ions are subjected to alkylation reaction with anthracene to generate a plurality of alkyl anthracene products with different substitution positions and different alkyl numbers and structures, but the alkyl anthracene products are influenced by the stability of the carbonium ions and the stability of the anthracene alkyl substitution products, and the structures of the products mainly adopt a thermodynamically stable structure and show specific distribution and composition.
According to the present invention, during the reaction with alkylating reagents having different carbon numbers, it is possible to obtain alkyl anthracene compositions (I) to (V) having different compositions of alkyl substituents by controlling the reaction, and the alkyl anthracene compositions (I) to (V) are obtained by separation by matching. The product structural characteristics and composition distribution are regulated based on control reaction, and the product purity is controlled by means of separation. The directional preparation of the alkyl anthracene composition can be achieved by a two-step process.
According to the present invention, the presence of a small amount of anthracene as an impurity in the alkyl anthracene composition is tolerated without affecting the alkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6) and oxidation reaction. Wherein, the composition C is prepared from anthracene and alkyl anthracene14+nH10+2n(2. ltoreq. n. ltoreq.6) based on the total weight of the alkyl anthracene composition C14+nH10+2nThe content of (2. ltoreq. n.ltoreq.6) is not less than 90% by weight, more preferably not less than 95% by weight, still more preferably not less than 98% by weight.
According to the present invention, it is preferable that,
molecular formula C16H14The alkyl anthracene is anthracene ring connected with 1 ethyl;
molecular formula C17H16The alkyl anthracene is anthracene ring connected with 1 propyl;
molecular formula C18H18The alkyl anthracene of (A) is anthracene ring connected with 1 butyl or 2 ethyl;
molecular formula C19H20The alkyl anthracene of (a) is an anthracene ring linked to 1 pentyl group, or to 1 ethyl group and 1 propyl group;
molecular formula C20H22The alkyl anthracene of (a) is an anthracene ring attached to 1 hexyl group, or to 1 ethyl group and 1 butyl group, or to 2 propyl groups.
According to the invention, the alkyl substituent in the alkyl substituent of the anthracene may be selected from ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, tert-pentyl, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 2-dimethylbutyl, 3-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-ethylbutyl, 1-dimethylpropyl, 1, 2-ethylpropyl, 3-dimethylbutyl, 2-ethylpentyl, 2-ethylbutyl, 1-ethylbutyl, 2-dimethylpropyl, 3-pentyl, 2-dimethylpropyl, 2-ethylpentyl, 2-dimethylpropyl, 2-pentyl, 2-dimethylpropyl, 2-ethylpentyl, 2, or N, N, 1, 1-dimethyl-2-methylpropyl, 1-methyl-2, 2-dimethylpropyl, 1-methyl-1-ethylpropyl and 1-ethyl-2-methylpropyl. Preferably, the alkyl substituents are selected from one or more of ethyl, isopropyl, 1-methylpropyl, tert-butyl, 1-methylbutyl, tert-pentyl, 1-ethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1-ethylbutyl, 1-dimethyl-2-methylpropyl, 1-methyl-2, 2-dimethylpropyl, 1-methyl-1-ethylpropyl and 1-ethyl-2-methylpropyl.
According to the present invention, the position of the alkyl substituent containing 2 to 3 carbon atoms is preferably in the alpha and/or beta position of the anthracycline, more preferably in the beta position of the anthracycline; the position of the alkyl substituent containing 4 to 6 carbon atoms is preferably in the beta position of the anthracycline.
According to mode a, as shown in fig. 1, the alkyl anthracene composition is contacted with an oxidizing agent in a manner that: and (3) separating the alkyl anthracene composition from the anthracene alkylation reaction product, and contacting the raw material liquid of the separated alkyl anthracene composition, the oxidation catalyst and the oxidation reaction solvent with an oxidant for oxidation reaction to obtain the alkyl anthraquinone composition. The anthracene alkylation reaction product contains light components having a boiling point lower than that of anthracene, optionally anthracene, and an alkyl anthracene material containing the alkyl anthracene composition. Thus, the process further comprises separating the alkyl anthracene composition from the anthracene alkylation reaction product.
As shown in fig. 1, mode 1:
the content of anthracene in the mixture with the boiling point being more than or equal to that of anthracene in the alkylation reaction product is less than or equal to 1 weight percent, and preferably, the content of anthracene in the mixture with the boiling point being more than or equal to that of anthracene in the alkylation reaction product is less than or equal to 5 weight percent;
the separation method comprises the following steps:
pre-separation: separating light components with boiling points lower than that of anthracene to obtain an alkyl anthracene system;
separation of alkyl anthracene composition: separating the alkyl anthracene composition C from the alkyl anthracene system by distillation14+ nH10+2nN is more than or equal to 2 and less than or equal to 6; or,
as shown in fig. 1 and 3, mode 2:
the content of anthracene in the mixture with the boiling point being more than or equal to that of anthracene in the alkylation reaction product is more than or equal to 10 weight percent, and preferably, the content of anthracene in the mixture with the boiling point being more than or equal to that of anthracene in the alkylation reaction product is more than 5 weight percent;
the separation method comprises the following steps:
pre-separation: separating light components with boiling points lower than that of anthracene to obtain a mixture containing anthracene and an alkyl anthracene system;
distilling the solvent to assist in separating anthracene: distilling a mixture containing anthracene and an alkyl anthracene system in the presence of a distillation solvent, and collecting the alkyl anthracene system, wherein the distillation solvent is an organic solvent which can dissolve anthracene and has a boiling point of between 100 ℃ and 340 ℃ in the process of auxiliary separation of anthracene;
separation of alkyl anthracene composition: separating the alkyl anthracene composition C from the alkyl anthracene system by distillation14+ nH10+2n，2≤n≤6。
In the mixture of the alkylation reaction product with the boiling point being more than or equal to that of anthracene, the content of anthracene is more than 1 wt% and less than 10 wt%, and adopting any one separation mode of a mode 1 or a mode 2, preferably, in the mixture of the alkylation reaction product with the boiling point being more than or equal to that of anthracene, the content of anthracene is less than or equal to 5 wt%, and adopting the separation mode of the mode 1; in the mixture of the alkylation reaction product with the boiling point more than or equal to that of anthracene, the content of anthracene is more than 5 wt%, and the separation mode of the mode 2 is adopted.
According to the present invention, an alkyl anthracene composition is prepared from a starting anthracene by alkylation, the resulting anthracene alkylation product mixture containing the reaction solvent, alkylation catalyst, residual anthracene, alkyl anthracene material, and other byproducts. It is well known to those skilled in the art that, due to differences in reaction methods and conditions, if anthracene can be completely converted, the anthracene alkylation reaction product mixture is free of anthracene; if the anthracene is not fully converted, the anthracene alkylation reaction product mixture will contain a portion of the remaining anthracene. If the alkylating agent can be fully converted, but not fully converted to alkyl anthracene, the anthracene alkylation reaction product mixture will contain the side reaction products of the alkylating agent; if the alkylating agent is not fully converted and not fully converted to alkyl anthracene, the anthracene alkylation reaction product mixture will contain side reaction products of the alkylating agent and the alkylating agent. In the anthracene alkylation reaction product, the boiling points of the reaction solvent, the alkylating agent and the side reaction product of the alkylating agent are all lower than that of anthracene, so that the substances in the anthracene alkylation reaction product with the boiling point lower than that of anthracene are collectively called light components.
According to mode 1 of the present invention, if the content of anthracene in the mixture having a boiling point of not less than anthracene in the alkylation reaction product is not more than 1 wt%, preferably not more than 5 wt% in the mixture having a boiling point of not less than anthracene in the alkylation reaction product, the alkyl anthracene composition can be separated from an alkyl anthracene-containing system directly after separating a light component, and a small amount of anthracene impurity does not affect the properties of the alkyl anthracene composition, the separation method comprising:
pre-separation: separating light components with boiling points lower than that of anthracene to obtain an alkyl anthracene system;
separation of alkyl anthracene composition: separating the alkyl anthracene composition C from the alkyl anthracene system by distillation14+ nH10+2n，2≤n≤6。
According to the present invention, during the course of the anthracene alkylation reaction, owing to the reaction characteristics and the method, mode 1 separation of the light components and preferably the first separation of the alkylation catalyst results in a mixture of a plurality of alkyl anthracenes, i.e. alkyl anthracene systems containing the alkyl anthracene composition C required according to the invention14+nH10+2n(n is not less than 2 and not more than 6), other alkyl anthracene by-products and other high boiling point by-products. Therefore, it is necessary to separate the alkyl anthracene composition C from the alkyl anthracene system by a reduced pressure distillation method14+nH10+2n(2≤n≤6)。
According to the present invention, in the separation step of the alkyl anthracene composition according to mode 1, distillation conditions under which the alkyl anthracene composition is separated from the alkyl anthracene system by 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 200-; preferably, the pressure at the top of the column is from 0.05 to 10kpa, the temperature at the bottom of the column is from 210 ℃ to 340 ℃, 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.
According to mode 2 of the present invention, if the content of anthracene in the mixture having a boiling point equal to or greater than that of anthracene in the alkylation reaction product is greater than or equal to 10% by weight, preferably greater than 5% by weight, after the separation of the light components, it is necessary to first separate the anthracene and then separate the alkyl anthracene composition.
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 ℃, the anthracene with a high melting point is separated by singly adopting a reduced pressure distillation technology, the operation difficulty is high, the pipeline is easy to block, and the continuous and stable operation of the process is seriously influenced. In addition, anthracene is very easily sublimed, and the sublimation process is difficult to control, and the chance that the pipeline takes place to block up is showing to increase. Therefore, it is impractical to separate the anthracene-alkyl anthracene system by simply using a vacuum distillation technique.
Accordingly, the present inventors propose a method for solvent-assisted separation of anthracene and distillation separation of alkyl anthracene-based mixtures. The alkyl anthracene damages 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, and the difficulty of subsequent distillation and separation is reduced. For this reason, the inventors of the present invention proposed to separate and remove anthracene, which has the highest melting point and is the most difficult to perform separation, by using a solvent-assisted distillation technique, and then separate the alkyl anthracene composition by distillation according to the difference in the boiling points to perform further separation.
According to one embodiment of the present invention, the distillation of solvent-assisted separation of anthracene is carried out in a distillation column, as shown in FIGS. 1 and 3. Specifically, after the preliminary separation, the mixture containing anthracene and an alkyl anthracene system is introduced into a distillation column, and the distillation process may be either batch or continuous. During distillation, a distillation solvent is introduced into the distillation tower, anthracene is gradually evaporated under the distillation condition, and simultaneously the introduced distillation solvent is also greatly gasified after entering the distillation tower and is evaporated together with the anthracene to enter a condenser at the top of the tower for condensation. In the molecular atmosphere of a large amount of gasified and liquefied distillation solvents, anthracene cannot be subjected to desublimation and solidification crystallization, but is dissolved in the distillation solvents to form a solution and flows along with the solution, and therefore the problem that the anthracene easily blocks a pipeline is solved. Part of solution formed by the distillation solvent and the anthracene reflows to enter a distillation tower for repeated distillation, and part of solution flows into a product tank at the top of the tower for collection. Through the introduction of the distillation solvent, the circulation of the distillation solvent between the tower top and the tower top condenser is controlled, and the feeding position, the temperature and the dosage are regulated and controlled at the same time, so that the solution formed by dissolving anthracene is extracted together smoothly, the high-efficiency separation of anthracene can be realized, and the problem of high condensation tendency during anthracene distillation can be solved.
Therefore, according to the invention, in the distillation solvent assisted separation process of anthracene, the distillation solvent is an organic solvent which can dissolve anthracene and has a boiling point of between 100 ℃ and 340 ℃ in the distillation solvent assisted separation process of anthracene.
Preferably, the distillation solvent is an organic solvent with a boiling point between 200-340 ℃, more preferably selected from C12-C19And/or one or more of linear and/or branched alkanes, halogenated hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters, and ethers. More preferably, the alkane is C12-C17And (b) one or more of a linear alkane and/or a branched alkane. More preferably, the halogenated hydrocarbon is selected from trichlorobenzene, tetrachlorobenzene, tribromobenzene, tetrabromobenzene, chlorinated C10-C18Alkane and bromo C10-C18One or more of alkanes. More preferably, the aromatic hydrocarbon is an alkyl substituent of benzene, and the total carbon number of the substituted alkyl is 4-12; further preferred is one or more of butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene, dodecylbenzene, triethylbenzene, tetraethylbenzene, dipropylbenzene, tripropylbenzene, dibutylbenzene, and dipentylbenzene. More preferably, the arene alkyl is a benzene substituent, and further preferably one or more of diphenylmethane and an alkyl substituent thereof, and diphenylethane and an alkyl substituent thereof; more preferably one or more of diphenylmethane, methyldiphenylmethane and 1, 2-diphenylethane. More preferably, the arene alkane is naphthalene and/or alkyl substituent of the naphthalene, and the total carbon number of the substituted alkyl of the naphthalene is 1-4; further preferred is one or more of naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, diethylnaphthalene, propylnaphthalene, methylethylnaphthalene and butylnaphthalene. More preferably, the alcohol is selected from one or more of benzyl alcohol, glycerol, diethylene glycol, triethylene glycol and tetraethylene glycol. More preferably, the ketone is selected from one or more of 1,1, 3-trimethylcyclohexenone, N-methylpyrrolidone and 1, 3-dimethyl-2-imidazolidinone. More preferably, the ester is selected from the group consisting of a dicarboxylic acid ester, ethyl benzoate, dimethyl phthalate, dibutyl phthalate, ethylene glycol carbonate, propylene glycol carbonate and phosphorusOne or more of trioctyl acid. More preferably, the ether is selected from one or more of ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diphenyl ether and sulfolane.
In embodiment 2, as shown in fig. 3, the conditions for distilling the solvent-assisted separation of anthracene include: the pressure at the top of the distillation tower is 0.5-40kpa, the temperature at the bottom of the distillation tower is 200-400 ℃, the number of theoretical plates is 12-55, and the reflux ratio at the top of the distillation tower is 0.1-4; preferably, the pressure at the top of the distillation column is 1-20kpa, the temperature at the bottom of the distillation column is 230-350 ℃, the number of theoretical plates is 16-50, and the reflux ratio at the top of the distillation column is 0.2-1. The amount of the distillation solvent to be used may be selected depending on the content of anthracene in the mixture containing anthracene and an alkyl anthracene system to be distilled, so that anthracene can be sufficiently separated to improve the purity of the alkyl anthracene system. Preferably, the mass ratio of the distilled solvent to the anthracene is 0.1:1 to 30: 1. Under the condition of ensuring that satisfactory purity of the alkyl anthracene system can be obtained, the mass ratio of the distilled solvent to the anthracene is 1:1 to 15:1 from the viewpoint of further reducing the cost of the method of the present invention.
According to the invention, in the process of distilling solvent to assist in separating anthracene, the product collected at the top of the tower is a mixture of the distilling solvent and anthracene, and the two need to be separated completely or partially. Preferably, the step of distilling the solvent to assist in separating the anthracene may further comprise: and collecting a mixture containing anthracene and the distilled solvent, separating the anthracene from the distilled solvent, recovering the anthracene, and repeatedly recycling the distilled solvent. Separation of anthracene from a mixture of distilled solvent and anthracene and distillation of the solvent can be carried out by a method including extraction and crystallization, depending on the difference in solubility; distillation may also be used depending on the difference in boiling points.
According to the present invention, it is preferable to separate the distilled solvent and anthracene by distillation. The distillation may be carried out using various distillation apparatus known in the art, for example: a sieve tray column or a packed column, more preferably a packed column. Specifically, a mixture containing anthracene and a distillation solvent is subjected to distillation under conditions including: the pressure at the top of the tower is 1-100kpa, the temperature at the bottom of the tower is 160-350 ℃, the number of theoretical plates is 6-40, and the reflux ratio at the top of the tower is 0.1-3; further preferably, the pressure at the top of the column is 20 to 60kpa, the temperature at the bottom of the column is 200 ℃ to 310 ℃, the number of theoretical plates is 8 to 30, and the reflux ratio at the top of the column is 0.2 to 2.
According to the present invention, after separating the light components and the catalyst and removing the anthracene remaining from the reaction in the mode 2 during the anthracene alkylation reaction, depending on the reaction characteristics and method, a mixture containing a plurality of alkyl anthracenes containing the alkyl anthracene composition C required in the present invention, that is, an alkyl anthracene system is obtained14+nH10+2n(n is not less than 2 and not more than 6), other alkyl anthracene by-products and other high boiling point by-products. Therefore, it is necessary to separate the alkyl anthracene composition C from the alkyl anthracene system by a reduced pressure distillation method14+nH10+2n(2≤n≤6)。
According to the present invention, in embodiment 2, as shown in fig. 3, in the separation step of the alkyl anthracene composition, the alkyl anthracene composition C is separated from the system containing alkyl anthracene by distillation14+nH10+2nAnd n is more than or equal to 2 and less than or equal to 6, and the 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 200-; preferably, the pressure at the top of the tower is 0.05-10kpa, 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.
According to the present invention, the anthracene alkylation reaction product contains, in addition to anthracene and an alkyl anthracene system containing the alkyl anthracene composition, light components having a boiling point lower than that of anthracene and an alkylation catalyst, which may be introduced or generated during the anthracene alkylation reaction in the previous step, due to the difference in the reaction method and the operation conditions. The light component having a boiling point lower than that of anthracene contains a reaction solvent for preparing an alkyl anthracene system by alkylation of anthracene, an alkylating agent, and a by-product produced by the alkylation (for example, the alkylating agent remaining after the alkylation and an alkylating agent by-product produced by a side reaction of the alkylating agent itself), and is collectively referred to as a light component. Therefore, a step of separating light components, i.e., a pre-separation step, is also included prior to the separation of the alkyl anthracene composition of mode 1 of the process for the preparation and separation of an alkyl anthracene composition, or prior to the distillation solvent-assisted separation of anthracene of mode 2.
According to the present invention, the method for separating light components may employ a separation method that is conventional in the art. Preferably, the light component in the mixture containing the anthracene and the alkyl anthracene system selectively contained is separated by a method of atmospheric or vacuum distillation from the viewpoint of further improving the separation efficiency and simplifying the operation.
According to an embodiment of the present invention, the preliminary separation is performed by a vacuum distillation method, in view of further improving the separation efficiency and simplifying the operation. Specifically, the method of pre-separating comprises: distilling a mixture containing a light component having a boiling point lower than that of anthracene, and an alkyl anthracene system containing the alkyl anthracene composition in a distillation column to obtain a distillate containing a light component having a boiling point lower than that of anthracene, and a bottom product containing anthracene and an alkyl anthracene system, under distillation conditions including: the distillation temperature is 50-350 ℃, preferably 60-300 ℃; the distillation pressure is from 0.1 to 20kpa, preferably from 0.5 to 15 kpa. In addition, the separated reaction solvent may be recycled or collected for disposal as required for the reaction.
According to the present invention, since the anthracene alkylation reaction product further contains an alkylation catalyst for preparing a series of alkyl anthracene products by subjecting anthracene to alkylation reaction, in order to ensure the separation effect of the subsequent steps, it is preferable that the preparation method further comprises separating the alkylation catalyst before the pre-separation in the mode 1 or the mode 2. The method of separating the alkylation catalyst may employ one or more separation methods conventional in the art, such as settling, filtration, and centrifugation.
According to the invention, an alkyl anthracene composition C obtained by alkylation of anthracene14+nH10+2n(2. ltoreq. n.ltoreq.6) as the target product, if it still contains other impurities, it can be further purified by other conventional separation methods or combined separation methods, including distillation, extraction and crystallization.
According to the invention, the preparation of the alkylanthraquinone compositions according to the invention, in particular of the alkylanthraquinone compositions (I) to (V), can also be effected in the B-mode. That is, alkyl anthracene series is prepared through anthracene alkylation reaction and then treatedOxidation to produce alkylanthraquinone series, i.e. oxidation of a mixture containing anthracene and alkylanthraquinone series selectively contained, controlling the oxidation reaction conditions to maximize the amount of anthracene and alkylanthraquinone series C selectively contained14+nH10+2n(2. ltoreq. n.ltoreq.20) is converted wholly or largely into anthraquinone and alkylanthraquinone systems C14+nH8+2nO2(n is not less than 2 and not more than 20), and separating the alkylanthraquinone composition C from the alkylanthraquinone system14+nH8+2nO2(2. ltoreq. n.ltoreq.6), in particular the alkylanthraquinone compositions (I) to (V).
Specifically, according to one embodiment of mode B, as shown in fig. 2, the alkyl anthracene composition is contacted with an oxidizing agent in a manner that: contacting a mixture of an anthracene alkylation reaction product containing the alkyl anthracene composition, an oxidation catalyst, and optionally an oxidation reaction solvent, with an oxidizing agent for oxidation to produce an alkyl anthracene oxidation product containing the alkyl anthraquinone composition, and separating the alkyl anthraquinone composition from the alkyl anthracene oxidation product. Preferably, the alkylation catalyst in the anthracene alkylation reaction product is separated and the alkylation reaction solvent is separated or not separated to obtain an alkylation product mixture containing a light component having a boiling point lower than that of anthracene, optionally containing anthracene, and an alkyl anthracene system containing the alkyl anthracene composition, the mixture of the alkylation product mixture, the oxidation catalyst, and optionally containing the oxidation reaction solvent is contacted with an oxidizing agent to perform an oxidation reaction to obtain an alkyl anthracene oxidation product containing the alkyl anthraquinone composition, and the alkyl anthraquinone composition is separated from the alkyl anthracene oxidation product.
As shown in fig. 2, the alkyl anthracene oxidation product contains materials having a boiling point lower than that of anthraquinone, and optionally anthraquinone and alkyl anthraquinone systems containing the alkyl anthraquinone composition, and thus, the method further comprises separating the alkyl anthraquinone composition from the alkyl anthracene oxidation product.
Mode 3:
the content of anthraquinone in the mixture with the boiling point being more than or equal to that of anthraquinone in the alkyl anthracene oxidation product is less than or equal to 1 weight percent, preferably, the content of anthraquinone in the mixture with the boiling point being more than or equal to that of anthraquinone in the alkyl anthracene oxidation product is less than or equal to 5 weight percent;
the separation method comprises the following steps:
pre-separation: separating the substances with the boiling points lower than that of the anthraquinone to obtain an alkyl anthraquinone system;
isolation of the alkylanthraquinone composition: separating the said alkylanthraquinone composition C from the alkylanthraquinone system by distillation14+nH8+2nO2，2≤n≤6；
Mode 4:
the content of anthraquinone in the mixture with the boiling point being more than or equal to 10 wt% of the oxidation product of the alkyl anthracene, preferably, the content of anthraquinone in the mixture with the boiling point being more than or equal to 5 wt% of the oxidation product of the alkyl anthracene;
the separation method comprises the following steps:
pre-separation: separating the substances with the boiling point lower than that of the anthraquinone to obtain a mixture containing the anthraquinone and the alkyl anthraquinone systems;
anthraquinone separation: the method for separating the anthraquinone is selected from one or more of extraction separation, melting crystallization separation of the anthraquinone, solvent crystallization separation of the anthraquinone and distillation separation of the anthraquinone, preferably distillation separation of the anthraquinone, and further preferably distillation solvent auxiliary separation of the anthraquinone: distilling a mixture containing anthraquinone and an alkylanthraquinone system in the presence of a distillation solvent, and collecting the alkylanthraquinone system, wherein the distillation solvent is an organic solvent which can dissolve the anthraquinone and has a boiling point of between 100 ℃ and 340 ℃ in the process of assisting in separating the anthraquinone;
isolation of the alkylanthraquinone composition: separation of the alkylanthraquinone composition C from the alkylanthraquinone System by distillation14+ nH8+2nO2，2≤n≤6。
According to the invention, the alkyl anthracene oxidation product contains substances with a boiling point lower than that of anthraquinone, and optionally anthraquinone and alkyl anthraquinone systems and other by-products. Preparing anthracene alkylation product from raw material anthracene through alkylation reaction, and separating alkylation catalyst and alkylation reaction solvent to obtain anthracene alkylation productAlkylation product mixture of alkyl anthracene series C14+nH10+2n(n is more than or equal to 2 and less than or equal to 20) is oxidized to obtain an alkyl anthraquinone system C14+nH8+2nO2(n is more than or equal to 2 and less than or equal to 20). After the anthracene and the alkyl anthracene in the reaction liquid are oxidized, the oxidation reaction conditions are controlled, and the anthracene and the alkyl anthracene are converted into anthraquinone and alkyl anthraquinone series C to the greatest extent or completely14+nH8+2nO2(2≤n≤20)。
According to the present invention, in the mode 3, if all or most of anthracene is converted by controlling the reaction method and conditions during the anthracene alkylation reaction of the raw material anthracene, the content of anthraquinone in the mixture of the alkyl anthracene oxidation product with the boiling point not less than the boiling point of anthraquinone is less than or equal to 1 wt%, preferably, the content of anthraquinone in the mixture of the alkyl anthracene oxidation product with the boiling point not less than the boiling point of anthraquinone is less than or equal to 5 wt%; the alkylanthraquinone composition C can be separated directly from the alkylanthraquinone-containing system after the light fraction has been separated off14+nH8+2nO2(2. ltoreq. n.ltoreq.6), small amounts of anthraquinone impurities do not affect the properties of the alkylanthraquinone composition.
According to the present invention, as described above, an alkylation reaction is carried out on anthracene as a raw material to produce an anthracene alkylation product, and the alkylation catalyst and the alkylation reaction solvent are separated to obtain an alkylation product mixture, wherein the alkyl anthracene is C14+nH10+2n(n is more than or equal to 2 and less than or equal to 20) to produce a mixture of a plurality of alkyl anthraquinones to obtain an alkyl anthraquinone system C14+nH8+2nO2(n is more than or equal to 2 and less than or equal to 20). The alkyl anthraquinone system contains the alkyl anthraquinone composition C required by the invention14+nH8+2nO2(2. ltoreq. n.ltoreq.6), and therefore, it is necessary to separate the alkylanthraquinone composition C from the alkylanthraquinone system by distillation under reduced pressure14+ nH8+2nO2(2≤n≤6)。
According to the invention, in the mode 3, in the step of separating the alkylanthraquinone composition, the alkylanthraquinone composition C is separated from the alkylanthraquinone system by distillation14+nH8+2nO2And n is more than or equal to 2 and less than or equal to 6, and the 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 230-; preferably, the pressure at the top of the column is from 0.05 to 10kpa, the temperature at the bottom of the column is from 240 ℃ to 370 ℃, 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.
According to the present invention, according to mode 4, if the anthracene is not completely converted during the anthracene alkylation reaction of the raw material anthracene by the alkylation reaction, the content of the anthraquinone in the mixture of the oxidation product of the alkyl anthracene having a boiling point equal to or higher than that of the anthraquinone is higher than or equal to 10% by weight, and preferably, the content of the anthraquinone in the mixture of the oxidation product of the alkyl anthracene having a boiling point equal to or higher than that of the anthraquinone is higher than 5% by weight, after the light components are separated, the anthraquinone needs to be separated and removed first, and then the composition of the alkyl anthraquinone needs to be separated.
Physical analysis revealed that the boiling point of anthraquinone was 377 ℃, and that the alkyl anthraquinone product and the anthraquinone homologue had a difference in boiling point between them, and the separation of the products was achieved by the vacuum distillation technique. However, the technical difficulty is that the melting point of the anthraquinone is as high as 286 ℃, the anthraquinone with high melting point is separated by singly adopting a reduced pressure distillation technology, the operation difficulty is high, the pipeline is easy to block, and the continuous and stable operation of the process is seriously influenced. In addition, anthraquinone is easy to sublimate, the sublimation process is difficult to control, and the possibility of blockage of the pipeline is obviously increased. Therefore, it is impractical to achieve separation of the anthraquinone-alkylanthraquinone product by simple distillation under reduced pressure.
Thus, similar to the process of anthracene and alkyl anthracene separation, the present inventors propose a solvent-assisted separation of anthraquinones and a distillation separation of alkyl anthraquinone systems. The existence of side chain substituent groups of the alkyl anthraquinone damages the regularity of the anthraquinone ring structure, so that the melting point of the alkyl anthraquinone product is obviously reduced, and the difficulty of subsequent distillation and separation is reduced. Therefore, the inventor of the present invention proposes to separate and remove the anthraquinone which has the highest melting point and is most difficult to separate by using a solvent-assisted distillation technology, and then further separate the high-boiling point alkyl anthraquinone system by using a reduced pressure distillation technology according to the difference of the boiling points.
According to one embodiment of the present invention, the distillation of the solvent-assisted separation of the anthraquinones is carried out in a distillation column, as shown in FIG. 4. Specifically, after the preliminary separation, the mixture containing the anthraquinones and the alkylanthraquinone system is introduced into a distillation column, which may be either batch or continuous. During distillation, a distillation solvent is introduced into the distillation tower, anthraquinone begins to be gradually evaporated under the distillation condition, and simultaneously the introduced distillation solvent also begins to be largely gasified after entering the distillation tower and is evaporated together with the anthraquinone to enter a condenser at the top of the tower for condensation. In the molecular atmosphere of a large amount of gasified and liquefied distilled solvent, anthraquinone can not be desublimated and solidified and crystallized, but is dissolved in the distilled solvent to form a solution which flows along with the solution, and further the problem that the pipeline is easily blocked by the anthraquinone is solved. Part of solution formed by the distillation solvent and the anthraquinone reflows to enter a distillation tower for repeated distillation, and part of solution flows into a product tank at the top of the tower for collection. Through the introduction of the distillation solvent, the circulation of the distillation solvent between the tower top and the tower top condenser is controlled, and the feeding position, the temperature and the dosage are regulated and controlled at the same time, so that the anthraquinone is dissolved to form a solution which is smoothly extracted together, the high-efficiency separation of the anthraquinone can be realized, and the problem of high condensation tendency during the distillation of the anthraquinone can be solved.
Therefore, according to the present invention, in the distillation solvent-assisted separation of anthraquinones, the distillation solvent is an organic solvent having a boiling point of 100-340 ℃ capable of dissolving anthraquinones in the assisted separation of anthraquinones.
Preferably, the distillation solvent is an organic solvent with a boiling point between 200-340 ℃, more preferably selected from C12-C19And/or one or more of linear and/or branched alkanes, halogenated hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters, and ethers. More preferably, the alkane is C12-C17And (b) one or more of a linear alkane and/or a branched alkane. More preferably, the halogenated hydrocarbon is selected from trichlorobenzene, tetrachlorobenzene, tribromobenzene, tetrabromobenzene, chlorinated C10-C18Alkane and bromo C10-C18One or more of alkanes. More preferably, the aromatic hydrocarbon is an alkyl substituent of benzene, and the total carbon number of the substituted alkyl is 4-12; more preferably butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, tert-butylbenzene,One or more of nonylbenzene, decylbenzene, undecylbenzene, dodecylbenzene, triethylbenzene, tetraethylbenzene, dipropylbenzene, tripropylbenzene, dibutylbenzene, and dipentylbenzene. More preferably, the arene alkyl is a benzene substituent, and further preferably one or more of diphenylmethane and an alkyl substituent thereof, and diphenylethane and an alkyl substituent thereof; more preferably one or more of diphenylmethane, methyldiphenylmethane and 1, 2-diphenylethane. More preferably, the arene alkane is naphthalene and/or alkyl substituent of the naphthalene, and the total carbon number of the substituted alkyl of the naphthalene is 1-4; further preferred is one or more of naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, diethylnaphthalene, propylnaphthalene, methylethylnaphthalene and butylnaphthalene. More preferably, the alcohol is selected from one or more of benzyl alcohol, glycerol, diethylene glycol, triethylene glycol and tetraethylene glycol. More preferably, the ketone is selected from one or more of 1,1, 3-trimethylcyclohexenone, N-methylpyrrolidone and 1, 3-dimethyl-2-imidazolidinone. More preferably, the ester is selected from one or more of the group consisting of a dicarboxylic acid ester, ethyl benzoate, dimethyl phthalate, dibutyl phthalate, ethylene glycol carbonate, propylene glycol carbonate and trioctyl phosphate. More preferably, the ether is selected from one or more of ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diphenyl ether and sulfolane.
In mode 4, the conditions for the distillation of the solvent-assisted separation of the anthraquinones include: the pressure at the top of the distillation tower is 0.5-40kpa, the temperature at the bottom of the distillation tower is 230-430 ℃, the number of theoretical plates is 12-55, and the reflux ratio at the top of the distillation tower is 0.1-4; preferably, the pressure at the top of the distillation tower is 1-20kpa, the temperature at the bottom of the distillation tower is 260-380 ℃, the theoretical plate number is 16-50, and the reflux ratio at the top of the distillation tower is 0.2-1. The amount of the distillation solvent to be used may be selected depending on the content of anthraquinone in the mixture containing anthraquinones and alkylanthraquinone series to be distilled, so that sufficient separation of anthraquinone can be achieved to improve the purity of alkylanthraquinone series. Preferably, the mass ratio of the distilled solvent to the anthraquinone is 0.1:1 to 30: 1. The mass ratio of the distilled solvent to the anthraquinone is 1:1 to 15:1 from the viewpoint of further reducing the cost of the method of the present invention under the condition that satisfactory purity of the alkylanthraquinone system can be ensured.
According to the invention, in the distillation solvent-assisted separation process of the anthraquinone, the product collected at the top of the tower is a mixture of the distillation solvent and the anthraquinone, and the distillation solvent and the anthraquinone are required to be completely or partially separated. Preferably, the step of distilling the solvent to assist in separating the anthraquinones may further comprise: collecting mixture containing anthraquinone and distilled solvent, separating anthraquinone and distilled solvent, recovering anthraquinone, and reusing distilled solvent. The separation of the anthraquinones from the mixture of the distilled solvent and the anthraquinones and the distilled solvent may be carried out by a method including extraction and crystallization depending on the difference in solubility; distillation may also be used depending on the difference in boiling points.
According to the present invention, it is preferable to separate the distilled solvent and the anthraquinones by distillation. The distillation may be carried out using various distillation apparatus known in the art, for example: a sieve tray column or a packed column, more preferably a packed column. Specifically, the mixture containing the anthraquinones and the distillation solvent is subjected to distillation under conditions including: the pressure at the top of the tower is 1-100kpa, the temperature at the bottom of the tower is 160-390 ℃, the number of theoretical plates is 6-40, and the reflux ratio at the top of the tower is 0.1-3; further preferably, the pressure at the top of the column is 20 to 60kpa, the temperature at the bottom of the column is 200 ℃ to 350 ℃, the number of theoretical plates is 8 to 30, and the reflux ratio at the top of the column is 0.2 to 2.
According to the present invention, as described above, an anthracene alkylation product is produced from a starting anthracene by an alkylation reaction, the alkylation catalyst is separated therefrom, and the mixture obtained with or without separation of the alkylation reaction solvent is obtained, wherein the alkyl anthracene compound is C14+nH10+2n(n is more than or equal to 2 and less than or equal to 20) to produce a mixture of a plurality of alkyl anthraquinones to obtain an alkyl anthraquinone system C14+nH8+2nO2(n is more than or equal to 2 and less than or equal to 20). The alkyl anthraquinone system contains the alkyl anthraquinone composition C required by the invention14+nH8+2nO2(2. ltoreq. n.ltoreq.6), and therefore, it is necessary to separate the alkylanthraquinone composition C from the alkylanthraquinone system by distillation under reduced pressure14+ nH8+2nO2(2≤n≤6)。
According to the present invention, in mode 4, in the step of separating the alkylanthraquinone composition, the alkylanthraquinone compound is separated from the alkylanthraquinone system by distillationThe alkylanthraquinone composition C14+nH8+2nO2And n is more than or equal to 2 and less than or equal to 6, and the 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 230-430 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8; preferably, the pressure at the top of the tower is 0.05-10kpa, the temperature at the bottom of the tower is 240-370 ℃, the theoretical plate number is 30-75, and the reflux ratio at the top of the tower is 1-7.
According to the present invention, during the oxidation reaction of alkyl anthracene, other substances having a boiling point lower than that of anthraquinone and an oxidation catalyst may be brought in or generated by different methods and operating conditions of the reaction. Wherein the substance having a boiling point lower than that of anthraquinone contains an oxidation reaction solvent and an oxidizing agent and oxidation reaction by-products, collectively referred to as light components. Thus, prior to the isolation of the alkylanthraquinone composition of mode 3, or prior to the isolation of the anthraquinone and alkylanthraquinone compositions of mode 4, a step of separating the light components, namely a pre-separation, is also included.
According to the present invention, the method for separating light components may employ a separation method that is conventional in the art. Preferably, the light fraction in the mixture containing the anthraquinone and optionally the anthraquinone and the alkylanthraquinone is separated by distillation under atmospheric pressure or reduced pressure from the viewpoint of further improving the separation efficiency and simplifying the operation.
According to a specific embodiment of the present invention, in the mode 3 or the mode 4, the method of pre-separation includes: distilling a mixture containing substances with the boiling point lower than that of anthraquinone, selectively containing anthraquinone and a system containing alkylanthraquinone to obtain a distillate containing substances with the boiling point lower than that of anthraquinone and a bottom product containing selectively containing anthraquinone and alkylanthraquinone systems, wherein the distillation conditions comprise: the distillation temperature is 50-390 ℃, preferably 60-340 ℃, and the distillation pressure is 0.1-20kpa, preferably 0.5-15 kpa. In addition, the separated light components can be recycled or collected for disposal according to the requirements of the reaction.
According to the present invention, since the alkyl anthracene oxidation product further contains an oxidation catalyst, in order to ensure the separation effect in the subsequent step, it is preferable that the method further comprises separating the oxidation catalyst before the preliminary separation in the mode 3 or the mode 4. The method of separating the oxidation catalyst may employ one or more separation methods conventional in the art, such as settling, filtration, and centrifugation.
According to the present invention, it is necessary to perform the oxidation reaction of the alkyl anthracene composition/the alkyl anthracene system containing the alkyl anthracene composition, regardless of the alkyl anthracene composition obtained by the a method or the alkyl anthracene system obtained by the B method.
According to the present invention, an alkyl anthracene composition is contacted with an oxidizing agent under oxidizing conditions and in the presence of an oxidation reaction solvent and an oxidation catalyst to undergo an oxidation reaction to produce an alkyl anthracene oxidation product containing an alkyl anthraquinone composition.
The mode of contacting the alkyl anthracene composition with the oxidizing agent and the oxidation catalyst according to the present invention may be various modes capable of achieving oxidation of the alkyl anthracene. Preferably, for more complete reaction, the contacting is carried out in the following manner: a raw material liquid containing an alkyl anthracene composition, an oxidation catalyst, and an oxidation reaction solvent is brought into contact with an oxidizing agent to carry out an oxidation reaction.
Specifically, in the mode a, the mode of contact is: the raw material liquid of the separated alkyl anthracene composition, the oxidation catalyst and the oxidation reaction solvent is contacted with an oxidizing agent to carry out an oxidation reaction.
Specifically, in the mode B, the mode of contact is: contacting a mixture of an anthracene alkylation reaction product containing the alkyl anthracene composition, an oxidation catalyst, and optionally an oxidation reaction solvent, with an oxidizing agent for oxidation to produce an alkyl anthracene oxidation product containing the alkyl anthraquinone composition, and separating the alkyl anthraquinone composition from the alkyl anthracene oxidation product.
Preferably:
mode 1C: the alkylation reaction solvent used in the anthracene alkylation reaction is the same as the oxidation reaction solvent used in the alkyl anthracene oxidation reaction, the alkylation catalyst in the anthracene alkylation reaction product is separated to obtain a light component with a boiling point lower than that of anthracene (in this case, the light component with a boiling point lower than that of anthracene contains the alkylation reaction solvent and other by-products with a boiling point higher than that of the alkylation reaction solvent but lower than that of anthracene), anthracene selectively contained and an alkylation product mixture of an alkyl anthracene system containing the alkyl anthracene composition, and the alkylation product mixture, the oxidation catalyst and an oxidizing agent are contacted for oxidation reaction to obtain an alkyl anthracene oxidation product containing the alkyl anthraquinone composition; or,
mode 2C: the alkylation reaction solvent used in the anthracene alkylation reaction is different from the oxidation reaction solvent used in the alkyl anthracene oxidation reaction, the alkylation catalyst and the alkylation reaction solvent in the anthracene alkylation reaction product are separated to obtain a light component with a boiling point lower than that of anthracene (at the moment, the light component with the boiling point lower than that of anthracene is a byproduct with a boiling point higher than that of the alkylation reaction solvent but lower than that of anthracene), selectively contained anthracene and an alkylation product mixture of an alkyl anthracene system, wherein the alkyl anthracene system contains the alkyl anthracene composition, and the mixture of the alkylation product mixture, the oxidation catalyst and the oxidation reaction solvent is contacted with an oxidizing agent to carry out oxidation reaction to obtain an alkyl anthracene oxidation product containing the alkyl anthraquinone composition.
According to the present invention, the oxidizing agent is generally hydrogen peroxide, and in the oxidation process, it is preferable to use hydrogen peroxide as the oxidizing agent in the form of an aqueous hydrogen peroxide solution for the 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 choice in the art.
According to the present invention, the oxidizing agent is used in an amount to effect oxidation of the alkyl anthracene to produce the alkyl anthraquinone during the oxidation process.
Specifically, in the mode a, the molar ratio of the oxidizing agent to the sum of all substances having an anthracycline structure in the separated alkyl anthracene composition is 0.01:1 to 100:1, preferably 1:1 to 50: 1.
Specifically, in the embodiment B, the molar ratio of the oxidizing agent to the alkylation product mixture (the alkylation product mixture containing the light component having a boiling point lower than that of anthracene, optionally contained anthracene, and an alkyl anthracene system obtained by separating the alkylation catalyst and selectively separating the alkylation reaction solvent), that is, the total of all substances having an anthracycline structure in the mixture containing the light component having a boiling point lower than that of anthracene, optionally contained anthracene, and an alkyl anthracene system, is 0.01:1 to 100:1, preferably 1:1 to 50: 1.
According to the invention, the oxidation catalyst is selected from one or more of oxides of alkaline earth metals, hydroxides of alkaline earth metals, oxygen-containing compounds of transition metals and oxygen-containing compounds of lanthanoid metals. Preferably, during the oxidation, the catalyst is selected from one or more of group IIA, group IVB, group VB, group VIB, group VIIB, group VIII metal oxygenates, lanthanide metal oxygenates. 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, it is further preferable that the oxidation of alkyl anthracene is effectively achieved by using the combination of the oxidizing agent hydrogen peroxide and one or more catalysts 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 lanthanoid metal, and that the oxidation system is simple and efficient, the separation and recovery of the catalyst is difficult, corrosion does not occur, and the equipment investment and the post-treatment cost of the oxidation waste liquid are reduced.
According to the present invention, the amount of the oxidizing agent and the amount of the oxidation catalyst used in the oxidation process can be selected from a wide range, and preferably, the molar ratio of the oxidizing agent to the oxidation 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.
In accordance with the present invention, the equipment, conditions and methods of the oxidation reaction in the oxidation process, in addition to the combination of the hydrogen peroxide oxidizing agent described above with a specific catalyst, can be carried out in a manner conventional in the art.
According to the invention, the place for carrying out the oxidation reaction by contacting the raw material liquid containing the alkyl anthracene composition, the oxidation catalyst and the oxidation reaction solvent with the oxidant can be any one of well-contacted and mixed reactors, including a kettle reactor and a tubular reactor, and any one or combination of a stirring kettle, a fixed bed, a moving bed, a fluidized bed, a supergravity reactor, a micro-scale reactor and a membrane reactor.
According to the present invention, in the oxidation process, the oxidation reaction generally occurs under conditions including: the reaction temperature is 10-200 ℃, and preferably 20-120 ℃; the reaction pressure is 0-1MPa, preferably 0-0.5 MPa; the reaction time is 0.01-48h, preferably 0.5-24 h.
According to the invention, in the oxidation process, the oxidation reaction solvent is an inert organic solvent capable of dissolving the alkyl anthracene. Wherein the oxidation reaction solvent is a solvent with a dielectric constant of 1-50 at 20 ℃, and the oxidation reaction solvent is C6And above, preferably C6-C12One or more of paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted, preferably one or more of monobasic, dibasic or polybasic substitutes of benzene; more preferably one or more of benzene multi-substituted compounds, the substituent is C1-C4Alkyl and halogen ofOne or more of the elements; more preferably, the oxidation reaction solvent is one or more of polyalkyl substituents of benzene; more preferably, the oxidation reaction solvent is one or more selected from the group consisting of 1,2, 3-trimethylbenzene, 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, and 1,2,3, 4-tetramethylbenzene; more preferably, the oxidation reaction solvent is one or more of aliphatic alcohol with 1-4 carbon atoms, tetrahydrofuran, acetone, ethyl acetate, acetonitrile, dimethyl sulfoxide, sulfolane, N-dimethylaniline, formamide, acetamide, N-alkyl substituted amide and N-alkyl pyrrolidone, wherein the number of alkyl substituents is 1-2, and each alkyl substituent is independently C1-C4Alkyl groups of (a); most preferably, the oxidation reaction solvent is selected from one or more of methanol, t-butanol, acetone, dimethyl sulfoxide, sulfolane, N-dimethylaniline, formamide, acetamide, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-methylpyrrolidone, and N-ethylpyrrolidone.
According to the present invention, the oxidation reaction solvent is used in an amount sufficient to ensure sufficient dissolution of the alkyl anthracene to provide a good reaction medium during the oxidation.
Specifically, in the mode a, the content of the separated alkyl anthracene composition is 0.1 to 80% by weight, preferably 5 to 50% by weight, based on the total weight of the separated alkyl anthracene composition and the oxidation reaction solvent.
Specifically, in the mode B, if the alkylation reaction solvent used in the anthracene alkylation reaction is the same as the oxidation reaction solvent used in the alkyl anthracene oxidation reaction, the content of the mixture of the light components having a boiling point lower than that of anthracene (excluding the alkylation reaction solvent), optionally anthracene, and the alkylation product of an alkyl anthracene system is 0.1 to 80% by weight, preferably 5 to 50% by weight, based on the total weight of the reaction liquid remaining after the separation of the alkylation catalyst.
Specifically, in the mode B, if the alkylation reaction solvent used in the anthracene alkylation reaction is different from the oxidation reaction solvent used in the alkyl anthracene oxidation reaction, the content of the alkylation reaction product mixture is 0.1 to 80% by weight, preferably 5 to 50% by weight, based on the total weight of the alkylation reaction solvent and the alkylation reaction solvent, which are separated to obtain the alkylation catalyst and the alkylation reaction solvent, and which contain the light component having a boiling point lower than that of anthracene, and the alkylation product mixture of anthracene and the alkyl anthracene system selectively contained therein.
According to the invention, an alkylanthraquinone composition C is obtained14+nH8+2nO2(2. ltoreq. n.ltoreq.6) as the target product, if it still contains other impurities, it can be further purified by other conventional separation methods or combined separation methods, including distillation, extraction and crystallization.
The present invention will be described in detail below by way of examples.
The material composition data are obtained by chromatographic analysis.
In the alkylation reaction of anthracene, the mass fraction x of each substance is expressed by the chromatographic peak area percentage of the substance, and the fraction W (mol%) of each substance based on the molar weight is calculated by combining the molar mass. AN represents anthracene, and Ci-AN represents alkyl anthracene with alkyl group having total carbon number i.
Conversion of Anthracene X1(mol%) is calculated as shown in formula 1:
alkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6) and the molecular formula is C16H14Is uniformly denoted as A1Molecular formula C17H16Is uniformly denoted as A2Molecular formula C18H18Is uniformly denoted as A3Molecular formula C19H20Is uniformly denoted as A4Molecular formula C20H22Is uniformly denoted as A5。
In the composition AiMass fraction of (3) GiThe calculation formula (wt%) is shown in formula 2:
alkyl anthracene composition C14+nH10+2n(n is not less than 2 and not more than 6) the calculation formula of the selectivity S (mol%) is shown as the formula 3:
(II) in the separation process of the anthracene-alkyl anthracene mixture, 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 alkyl anthracene composition is B2All based on chromatographic data. The isolated yield of anthracene is defined as Y1The isolated yield of a certain alkyl anthracene composition is defined as Y2。
(III) defining the conversion rate of Ci-AN as X in the oxidation reaction process of alkyl anthracene2(mol%), the material selectivity calculated on 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 used for alkyl anthracene, Ci-AO is used for alkyl anthraquinone, and Ci-X is used for other byproducts.
The conversion of the alkyl anthracene composition is shown in formula 4:
the selectivity of the alkylanthraquinone composition is shown in formula 5:
the yield of the oxidation reaction of the alkylanthraquinone composition is shown in formula 6:
YCi-AO＝X2×SCi-AO (6)
the calculation method of the content of each substance in the alkyl anthraquinone composition is the same as that of each substance in the alkyl anthracene composition.
Examples 1-14 are provided to illustrate the alkyl anthracene composition, the method of preparation, and the method of separation provided herein. Comparative example 1 and example 7 illustrate the characteristics of the separation process provided by the present invention.
Example 1
Alkylation reaction
Anthracene and ethylene are alkylated, mesitylene is used as solvent, and methanesulfonic acid is used as catalyst. 173g of anthracene, 800ml of mesitylene and 22g of methanesulfonic acid were added to a stirred tank. After sealing, the temperature is raised to 120 ℃ at the rotation speed of 1000 rpm, and the pressure is 0.5 MPa. After the temperature reaches the requirement, 91g of ethylene is added into the kettle, and the feeding time is 6 hours. When the olefin feeding is finished, the reaction is continued for 6 hours while the reaction conditions are maintained, and then the reaction is terminated. Reacting for multiple batches under the same condition, and uniformly collecting reaction products as raw materials for separating alkyl anthracene after settling and separating the catalyst.
Analyzing the alkyl anthracene product with the molecular formula of C based on a reaction mechanism and a mass spectrum result16H14The material structure of (1) is that an anthracene ring is connected with an ethyl group (100 weight percent); molecular formula C18H18The material structure of (1) is that the anthracene ring is linked to 2 ethyl groups (56% by weight) and the anthracene ring is linked to 1 tert-butyl group (44% by weight); molecular formula C19H20The substance of (1) has the structure that an anthracene ring is connected with 1 tertiary amyl group (100 percent by weight); molecular formula of C20H22The material structure of (a) is that the anthracycline is linked to 1 ethyl group and 1 tert-butyl group (75 wt%), and the anthracycline is linked to 1 hexyl group (25 wt%).
(II) separation
Under the conditions of 3kpa (absolute pressure) and 60-150 ℃ of temperature, after substances with boiling points lower than that of anthracene are removed by distillation (the same applies below), the mixture of anthracene and alkyl anthracene is fed into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 250 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.25, and the mass ratio of the distilled solvent to anthracene was 3: 1. 2) Alkyl anthracene compositionsThe distillation conditions of (3): the pressure at the tower top is 1kpa, the temperature at the tower bottom is 245 ℃, the number of theoretical plates is 65, the reflux ratio at the tower top is 3, and the alkyl anthracene composition C is collected at the tower top14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 1.
Example 2
Alkylation reaction
Anthracene and propylene are alkylated, mesitylene is used as solvent, and methanesulfonic acid is used as catalyst. 173g of anthracene, 800ml of mesitylene and 22g of methanesulfonic acid were added to the stirred tank. After sealing, the temperature is raised to 120 ℃ at a rotation speed of 1000 rpm, and the pressure is 0.5 MPa. After the temperature reaches the requirement, 102g of propylene is added into the kettle, and the feeding time is 6 hours. When the olefin feeding is finished, the reaction is continued for 6 hours while the reaction conditions are maintained, and then the reaction is terminated. Reacting for multiple batches under the same condition, and uniformly collecting reaction products as raw materials for separating alkyl anthracene after settling and separating the catalyst.
Analyzing the alkyl anthracene product with the molecular formula of C based on a reaction mechanism and a mass spectrum result17H16The substance structure of (1) is that an anthracene ring is connected with isopropyl (100 weight percent); molecular formula C18H18The substance structure of (1) is that anthracene ring is connected with 1 tert-butyl (100 wt%); molecular formula C19H20The substance of (1) has the structure that an anthracene ring is connected with 1 tertiary amyl group (100 percent by weight); molecular formula of C20H22The material structure of (a) is that the anthracycline is linked to 2 isopropyl groups (74 wt.%), and the anthracycline is linked to 1 hexyl group (26 wt.%).
(II) separation
After substances with a boiling point lower than that of anthracene are removed by distillation,feeding the mixture of anthracene and alkyl anthracene into a distillation tower for continuous distillation, wherein the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 261 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.25, and the mass ratio of the distilled solvent to anthracene was 3: 1. 2) Separation of alkyl anthracene composition, distillation conditions: the pressure at the top of the tower is 1kpa, the temperature at the bottom of the tower is 267 ℃, the number of theoretical plates is 65, the reflux ratio at the top of the tower is 3, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 1.
Example 3
Alkylation reaction
Anthracene and isobutene are alkylated, mesitylene is used as a solvent, and methanesulfonic acid is used as a catalyst. 173g of anthracene, 800ml of mesitylene and 22g of methanesulfonic acid were added to the stirred tank. After sealing, the temperature is raised to 120 ℃ at a rotation speed of 1000 rpm, and the pressure is 0.5 MPa. After the temperature reaches the requirement, 27g of isobutene is added into the kettle, and the feeding time is 6 hours. When the olefin feeding is finished, the reaction is continued for 6 hours while the reaction conditions are maintained, and then the reaction is terminated. Reacting for multiple batches under the same condition, and uniformly collecting reaction products as raw materials for separating alkyl anthracene after settling and separating the catalyst.
Analyzing the alkyl anthracene product with the molecular formula of C based on a reaction mechanism and a mass spectrum result17H16The substance structure of (1) is that an anthracene ring is connected with isopropyl (100 weight percent); molecular formula C18H18The substance structure of (1) is that anthracene ring is connected with 1 tert-butyl (100 wt%); molecular formula of C19H20Has the material structure ofThe anthracene ring is attached to 1 tert-amyl group (100% by weight); molecular formula C20H22The material structure of (a) is an anthracene ring with 1 hexyl group attached (100 wt%).
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 245 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.25, and the mass ratio of the distilled solvent to anthracene was 3: 1. 2) Separation of alkyl anthracene composition, distillation conditions: the pressure at the top of the tower is 1kpa, the temperature at the bottom of the tower is 258 ℃, the number of theoretical plates is 65, the reflux ratio at the top of the tower is 3, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). Purity B of anthracene separated in step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 1.
Example 4
Alkylation reaction
The alkylation reaction of anthracene and 2-methyl-2-butylene takes mesitylene as solvent and methanesulfonic acid as catalyst. 173g of anthracene, 800ml of mesitylene and 27g of methanesulfonic acid were added to the stirred tank. After sealing, the temperature is raised to 120 ℃ at a rotation speed of 1000 rpm, and the pressure is 0.2 MPa. After the temperature reaches the requirement, 97g of pentene is added into the kettle, and the feeding time is 6 hours. When the olefin feeding is finished, the reaction is continued for 6 hours while the reaction conditions are maintained, and then the reaction is terminated. Reacting for multiple batches under the same condition, and uniformly collecting reaction products as raw materials for separating alkyl anthracene after settling and separating the catalyst.
Analysis based on reaction mechanism and mass spectrometry resultsThe alkyl anthracene product has the formula C17H16The substance structure of (1) is that an anthracene ring is connected with isopropyl (100 weight percent); molecular formula C18H18The material structure of (a) is that an anthracycline is linked to 1 tert-butyl group (100% by weight); molecular formula C19H20The substance of (1) has the structure that an anthracene ring is connected with 1 amyl (100 weight percent); molecular formula C20H22The material structure of (a) is an anthracene ring with 1 hexyl group attached (100 wt%).
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 270 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.25, and the mass ratio of the distilled solvent to anthracene was 3: 1. 2) Separation of alkyl anthracene composition, distillation conditions: the pressure at the top of the tower is 1kpa, the temperature at the bottom of the tower is 292 ℃, the number of theoretical plates is 65, the reflux ratio at the top of the tower is 3:1, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 1.
Example 5
Alkylation reaction
Anthracene and 2-methyl-2-pentenyl are alkylated, mesitylene is used as solvent, and methanesulfonic acid is used as catalyst. 173g of anthracene, 800ml of mesitylene and 27g of methanesulfonic acid were added to the stirred tank. After sealing, the temperature is raised to 120 ℃ at the rotation speed of 1000 rpm, and the pressure is 0.2 MPa. After the temperature reaches the requirement, 408g of hexene is added into the kettle, and the feeding time is 6 hours. When the olefin feeding is finished, the reaction is continued for 6 hours while the reaction conditions are maintained, and then the reaction is terminated. Reacting for multiple batches under the same condition, and uniformly collecting reaction products as raw materials for separating alkyl anthracene after settling and separating the catalyst.
Analyzing the alkyl anthracene product with the molecular formula of C based on a reaction mechanism and a mass spectrum result17H16The substance structure of (1) is that an anthracene ring is connected with isopropyl (100 weight percent); molecular formula of C18H18The substance structure of (1) is that anthracene ring is connected with 1 tert-butyl (100 wt%); molecular formula C19H20The substance of (1) has the structure that an anthracene ring is connected with 1 tertiary amyl group (100 percent by weight); molecular formula C20H22The material structure of (a) is an anthracene ring with 1 hexyl group attached (100 wt%).
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 285 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.25, and the mass ratio of the distilled solvent to anthracene was 3: 1. 2) Separation of alkyl anthracene composition, distillation conditions: the pressure at the top of the tower is 1kpa, the temperature at the bottom of the tower is 315 ℃, the number of theoretical plates is 65, the reflux ratio at the top of the tower is 3, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 1.
Example 6
Alkylation reaction
Anthracene and 2-methyl-2-butylene alkylation reaction, mesitylene is used as a solvent, and p-toluenesulfonic acid is used as a catalyst. Into a stirred tank were added 77g of anthracene, 800ml of mesitylene and 8g of p-toluenesulfonic acid. After sealing, the temperature is raised to 100 ℃ at a rotation speed of 1000 rpm, and the pressure is 0 MPa. And after the temperature reaches the requirement, 30g of pentene is added into the kettle, and the feeding time is 6 hours. When the olefin feeding is finished, the reaction is continued for 6 hours while the reaction conditions are maintained, and then the reaction is terminated. Reacting for multiple batches under the same condition, and after settling and separating the catalyst, uniformly collecting reaction products as raw materials for separating alkyl anthracene.
Analyzing the alkyl anthracene product with the molecular formula of C based on a reaction mechanism and a mass spectrum result17H16The substance structure of (1) is that an anthracene ring is connected with isopropyl (100 weight percent); molecular formula C18H18The substance structure of (1) is that anthracene ring is connected with 1 tert-butyl (100 wt%); molecular formula C19H20The substance of (1) has the structure that an anthracene ring is connected with 1 amyl (100 weight percent); molecular formula C20H22The material structure of (a) is an anthracene ring with 1 hexyl group attached (100 wt%).
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 240 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.3, and the mass ratio of the distilled solvent to anthracene was 10: 1. 2) Separation of alkyl anthracene composition, distillation conditions: the pressure at the top of the tower is 1kpa, the temperature at the bottom of the tower is 284 ℃, the number of theoretical plates is 55, the reflux ratio at the top of the tower is 4, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 1.
Example 7
Alkylation reaction
The alkylation reaction of anthracene and 2-methyl-2-butylene takes mesitylene as solvent and p-toluenesulfonic acid as catalyst. Into the stirred tank were added 297g of anthracene, 800ml of mesitylene and 174g of p-toluenesulfonic acid. After sealing, the temperature is raised to 140 ℃ at the rotation speed of 1000 rpm, and the pressure is 0.5 MPa. After the temperature reaches the requirement, 292g of pentene is added into the kettle, and the feeding time is 6 hours. When the olefin feeding is finished, the reaction is continued for 6 hours while the reaction conditions are maintained, and then the reaction is terminated. Reacting for multiple batches under the same condition, and uniformly collecting reaction products as raw materials for separating alkyl anthracene after settling and separating the catalyst.
Analyzing the alkyl anthracene product with the molecular formula of C based on a reaction mechanism and a mass spectrum result17H16The substance structure of (1) is that an anthracene ring is connected with isopropyl (100 weight percent); molecular formula of C18H18The substance structure of (1) is that anthracene ring is connected with 1 tert-butyl (100 wt%); molecular formula C19H20The substance of (1) has the structure that an anthracene ring is connected with 1 amyl (100 weight percent); molecular formula of C20H22The material structure of (a) is an anthracene ring with 1 hexyl group attached (100 wt%).
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 276 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.3, and the mass ratio of the distilled solvent to anthracene was 10: 1. 2) Separation of alkyl anthracene composition, distillation conditions: 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 55, the reflux ratio at the top of the tower is 4, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene compositionC14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 1.
Example 8
Alkylation reaction
The alkylation reaction of anthracene and 2-methyl-2-butylene takes mesitylene as solvent and p-toluenesulfonic acid as catalyst. 460g of anthracene, 800ml of mesitylene and 493g of p-toluenesulfonic acid are added into the stirring kettle. After sealing, the temperature is raised to 165 ℃ at the rotation speed of 1000 rpm, and the pressure is 1.0 MPa. After the temperature reached the requirement, 452g of pentene was added to the kettle over a 6 hour feed period. When the olefin feeding is finished, the reaction is continued for 6 hours while the reaction conditions are maintained, and then the reaction is terminated. Reacting for multiple batches under the same condition, and uniformly collecting reaction products as raw materials for separating alkyl anthracene after settling and separating the catalyst.
Analyzing the alkyl anthracene product with the molecular formula of C based on a reaction mechanism and a mass spectrum result17H16The material structure of (a) is that an anthracene ring is connected with isopropyl (100 weight percent); molecular formula C18H18The substance structure of (1) is that anthracene ring is connected with 1 tert-butyl (100 wt%); molecular formula C19H20The material structure of (a) is an anthracycline to which is attached 1 pentyl group (100% by weight); molecular formula C20H22The material structure of (a) is an anthracene ring with 1 hexyl group attached (100 wt%).
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 258 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.3, and the mass ratio of the distilled solvent to anthracene was 10: 1. 2) Alkyl anthraceneSeparation of the composition, distillation conditions: the pressure at the top of the tower is 1kpa, the temperature at the bottom of the tower is 316 ℃, the number of theoretical plates is 55, the reflux ratio at the top of the tower is 4, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 2.
Example 9
The alkylation reaction of step (one) was the same as in example 7.
(II) separation
After substances with a boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2, 4-trichlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 276 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.3, and the mass ratio of the distilled solvent to anthracene was 12: 1. 2) Separation of alkyl anthracene composition, distillation conditions: 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 55, the reflux ratio at the top of the tower is 4, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). Purity B of anthracene separated in step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in Table 2Shown in the figure.
Example 10
The alkylation reaction of step (one) was the same as in example 7.
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is diphenylmethane, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 259 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.3, and the mass ratio of the distilled solvent to anthracene was 15: 1. 2) Separation of alkyl anthracene composition, distillation conditions: 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 55, the reflux ratio at the top of the tower is 4, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Anthracene separation yield Y1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 2.
Example 11
The alkylation reaction of step (one) was the same as in example 7.
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 2, 7-dimethylnaphthalene, and the distillation conditions are as follows: the pressure at the top of the column was 8kpa, the temperature at the bottom of the column was 328 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.3, and the mass ratio of the distilled solvent to anthracene was 3: 1. 2) Separation of alkyl anthracene composition, distillation conditions: 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 55, the reflux ratio at the top of the tower is 4, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 2.
Example 12
The alkylation reaction of step (one) was the same as in example 7.
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 276 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.3, and the mass ratio of the distilled solvent to anthracene was 10: 1. 2) Separation of alkyl anthracene composition, distillation conditions: the pressure at the top of the tower is 1kpa, the temperature at the bottom of the tower is 305 ℃, the number of theoretical plates is 65, the reflux ratio at the top of the tower is 4, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 2.
Example 13
The alkylation reaction of step (one) was the same as in example 7.
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 276 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.3, and the mass ratio of the distilled solvent to anthracene was 10: 1. 2) Separation of alkyl anthracene composition, distillation conditions: the pressure at the top of the tower is 3kpa, the temperature at the bottom of the tower is 338 ℃, the number of theoretical plates is 55, the reflux ratio at the top of the tower is 4, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 2.
Example 14
The alkylation reaction of step (one) was the same as in example 7.
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) solvent-assisted separation of anthracene: the distillation solvent is 1,2,3, 4-tetrachlorobenzene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 276 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.3, and the mass ratio of the distilled solvent to anthracene was 10: 1. 2) Separation of alkyl anthracene composition, distillation conditions: 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 40, the reflux ratio at the top of the tower is 3, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 2.
Comparative example 1
Alkylation reaction
The alkylation reaction of anthracene and 2-methyl-2-butylene takes mesitylene as solvent and p-toluenesulfonic acid as catalyst. Into the stirred tank were added 297g of anthracene, 800ml of mesitylene and 174g of p-toluenesulfonic acid. After sealing, the temperature is raised to 140 ℃ at the rotation speed of 1000 rpm, and the pressure is 0.5 MPa. After the temperature reaches the requirement, 292g of pentene is added into the kettle, and the feeding time is 6 hours. When the olefin feeding is finished, the reaction is continued for 6 hours while the reaction conditions are maintained, and then the reaction is terminated. Reacting for multiple batches under the same condition, and uniformly collecting reaction products as raw materials for separating alkyl anthracene after settling and separating the catalyst.
Analyzing the alkyl anthracene product with the molecular formula of C based on a reaction mechanism and a mass spectrum result17H16The substance structure of (1) is that an anthracene ring is connected with isopropyl (100 weight percent); molecular formula C18H18The substance structure of (1) is that anthracene ring is connected with 1 tert-butyl (100 wt%); molecular formula C19H20The substance of (1) has the structure that an anthracene ring is connected with 1 amyl (100 weight percent); molecular formula C20H22The material structure of (a) is an anthracene ring with 1 hexyl group attached (100 wt%).
(II) separation
After substances with the boiling point lower than that of anthracene are removed by distillation, the mixture of anthracene and alkyl anthracene is sent into a distillation tower for continuous distillation, and the material flow is 10 g/min. 1) And (3) direct distillation separation of anthracene: distillation conditions: the overhead pressure was 3kpa, the bottom temperature was 276 ℃, the number of theoretical plates was 40, and the overhead reflux ratio was 0.3. 2) Separation of alkyl anthracene composition, distillation conditions: the pressure at the top of the column is 1kpa, the temperature at the bottom of the column is 310 ℃, andthe number of theoretical plates is 55, the reflux ratio at the top of the tower is 4, and the alkyl anthracene composition C is collected at the top of the tower14+nH10+2n(2≤n≤6)。
Conversion rate X of anthracene in the step (I)1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) composition GiAlkyl anthracene composition C14+nH10+2n(n is more than or equal to 2 and less than or equal to 6). The purity B of the anthracene separated in the step (II)1Alkyl anthracene composition C14+ nH10+2n(2. ltoreq. n. ltoreq.6) purity B2Separation yield Y of anthracene1Alkyl anthracene composition C14+nH10+2n(2. ltoreq. n. ltoreq.6) separation yield Y2As shown in table 1.
Examples 15-30 are provided to illustrate the alkylanthraquinone compositions provided by the present invention and the method of making the same, and comparative example 2 is provided to compare the performance of the alkylanthraquinone composition of example 18 with that of a single anthraquinone when made into a working fluid.
Example 15
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 1. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 303g of potassium chromate were charged into a reaction vessel. The reaction is carried out at the normal pressure of 100 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The alkylanthraquinone composition had an oxidation yield of 98.36 mole% and the composition is shown in Table 3. The alkyl substituent structure and substitution position of the oxidation product alkyl anthraquinone (anthraquinone parent nucleus is 9, 10-anthraquinone) are the same as those of the corresponding alkyl anthracene, and the following is the same.
Example 16
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 2. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 270g of lanthanum nitrate hexahydrate are added into a reaction kettle. The reaction is carried out at the normal pressure of 100 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The alkylanthraquinone composition had an oxidation yield of 98.71 mole% and the composition is shown in Table 3.
Example 17
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 3. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 214g of sodium molybdate were charged into a reaction vessel. The reaction is carried out at the normal pressure of 100 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The alkylanthraquinone composition had an oxidation yield of 98.02 mole% and the composition is shown in Table 3.
Example 18
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 4. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of tert-butyl alcohol and 128g of zirconium dioxide were added to a reaction vessel. The reaction is carried out at the normal pressure of 80 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The alkylanthraquinone composition had an oxidation yield of 99.2 mole% and the composition is shown in Table 3.
Example 19
The step (I) anthracene alkylation reaction was separated from the step (II) as in example 5. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of tert-butyl alcohol and 303g of potassium chromate were added to a reaction kettle. The reaction is carried out at the normal pressure of 80 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The alkylanthraquinone composition had an oxidation yield of 98.88 mole% and the composition is shown in Table 3.
Example 20
The step (I) anthraalkylation reaction and the step (II) separation are the same as in example 6. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 214g of sodium molybdate were charged into a reaction vessel. The reaction is carried out at the normal pressure of 100 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The alkylanthraquinone composition had an oxidation yield of 99.35 mole% and the composition is shown in Table 3.
Example 21
The step (one) anthracene alkylation reaction was separated from the step (two) as in example 7. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 214g of sodium molybdate were charged into a reaction vessel. The reaction is carried out at the normal pressure of 100 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The alkylanthraquinone composition had an oxidation yield of 99.01 mole% and the composition is shown in Table 3.
Example 22
The step (I) anthraalkylation reaction and the step (II) separation were the same as in example 8. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 214g of sodium molybdate were charged into a reaction vessel. The reaction is carried out at the normal pressure of 100 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The alkylanthraquinone composition had an oxidation yield of 99.27 mole% and the composition is shown in Table 3.
TABLE 3
Example 23
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 4. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of tert-butyl alcohol and 128g of zirconium dioxide were added to a reaction vessel. The reaction is carried out at the normal pressure of 80 ℃, 1768g of hydrogen peroxide (the content of hydrogen peroxide is 30 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The oxidation reaction yield of the alkylanthraquinone composition was 90.65 mol%.
Example 24
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 4. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 500g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 840g of sodium molybdate were charged into a reaction vessel. The reaction is carried out at the normal pressure of 100 ℃, 4161g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The oxidation reaction yield of the alkylanthraquinone composition was 67.8 mol%.
Example 25
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 4. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N, N-dimethylformamide and 303g of potassium chromate were added to a reaction vessel. The reaction is carried out at the normal pressure of 100 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The oxidation reaction yield of the alkylanthraquinone composition was 97.72 mole%.
Example 26
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 4. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 353g of potassium chromate were charged into a reaction vessel. The reaction is carried out at the normal pressure of 65 ℃, 1238g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The oxidation reaction yield of the alkylanthraquinone composition was 54.36 mol%.
Example 27
The step (I) of the anthracene alkylation reaction and the step (II) of the separation are the same as those in example 4. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 135g of lanthanum nitrate hexahydrate are added into a reaction kettle. The reaction is carried out at the normal pressure of 100 ℃, 530g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The oxidation reaction yield of the alkylanthraquinone composition was 45.6 mol%.
Example 28
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 4. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkyl anthracene composition, 2000g of N-methylpyrrolidone and 214g of sodium molybdate were charged into a reaction vessel. The reaction is carried out at the normal pressure of 100 ℃, 1061g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 3 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The oxidation reaction yield of the alkylanthraquinone composition was 67.38 mol%.
Example 29
Step (one) was the same as in example 4. After the reaction is finished, separating out the catalyst and the substance with the boiling point less than that of the anthracene, and then sending the mixture of the anthracene and the alkyl anthracene into the step (II) together for oxidation reaction.
(di) oxidation reaction
And (2) adding the mixture of anthracene and alkyl anthracene obtained in the step (one) into a reaction kettle, and adding 3478g of N-methyl pyrrolidone and 400g of sodium molybdate. The reaction is carried out at the normal pressure of 100 ℃, 1979g of hydrogen peroxide (the content of hydrogen peroxide is 50 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. And (3) separating out the catalyst and substances with the boiling point less than that of the anthraquinone after the reaction is finished to obtain a mixture of the anthraquinone and the alkylanthraquinone, and sending the mixture to the step (three) for separation. The total yield of the oxidation reaction of anthraquinone and alkylanthraquinone was 95.6 mol%.
(III) separation Process
Separating the mixture of anthraquinones and alkylanthraquinones to obtain an alkylanthraquinone composition.
The mixture of anthraquinone and alkylanthraquinone is fed into a distillation column for continuous distillation, the material flow is 10 g/min. 1) Solvent-assisted separation of anthraquinones: the distillation solvent is 2, 7-dimethylnaphthalene, and the distillation conditions are as follows: the pressure at the top of the column was 3kpa, the temperature at the bottom of the column was 298 ℃, the number of theoretical plates was 40, the reflux ratio at the top of the column was 0.25, and the mass ratio of the distilled solvent to anthracene was 3: 1. 2) Separation of the alkylanthraquinone composition, distillation conditions: the pressure at the top of the tower is 1kpa, the temperature at the bottom of the tower is 326 ℃, the number of theoretical plates is 65, the reflux ratio at the top of the tower is 3, and the alkyl anthraquinone composition C is collected at the top of the tower14+nH8+2nO2(n is more than or equal to 2 and less than or equal to 6). And (3) separating results: the purity of the alkylanthraquinone composition was 96.38% by weight and the isolation yield was 94.12% by weight.
Example 30
The step (I) of the anthracene alkylation reaction was separated from the step (II) as in example 4. And oxidizing the separated alkyl anthracene composition serving as a raw material to prepare the alkyl anthraquinone composition.
(III) oxidation reaction.
The alkyl anthracene composition is oxidized to produce an alkyl anthraquinone composition. 127g of an alkylanthracene composition, 2000g of methanol and 264g of 36% by weight hydrochloric acid were charged into a reaction vessel. The reaction is carried out at the normal pressure of 65 ℃, 295g of hydrogen peroxide (the content of hydrogen peroxide is 30 weight percent) is added into the kettle through a peristaltic pump, and the total feeding time is 8 hours. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. The oxidation reaction yield of the alkylanthraquinone composition was 98.15 mol%.
Comparative example 2
Two kinds of alkyl anthraquinone working liquid, A and B, are prepared at normal temperature (30 ℃). The mixed solvent is mesitylene and diiso-tert-butyl methanol with the volume ratio of 3: 2.
The anthraquinone carrier of working fluid A was the alkylanthraquinone composition of example 18, wherein C17H14O21.89 wt%, C18H16O225.14 wt.%, C19H18O261.02 wt.% of C20H20O211.88% by weight of C14H8O2Accounting for 0.07 wt%. The total content of the alkyl anthraquinone in the working solution A is 0.78 mol/L.
The anthraquinone carrier of the working solution B is 2-tert-amylanthraquinone and 2-sec-amylanthraquinone, and the molar ratio of the two is 3: 1. The content of amylanthraquinone in the working solution B is 0.65 mol/L.
And respectively adopting the working solution A and the working solution B to carry out intermittent stirred tank hydrogenation, and measuring the limit hydrogenation efficiency (limit hydrogen efficiency for short) of the working solution. The adding amount of the working solution is 120ml, and the catalyst is Pd/Al2O3(Pd content: 1.8% by weight) was added in an amount of 0.6g, the reaction temperature was 60 ℃ and the pressure of hydrogen in the reactor was 0.3 MPa. And continuously introducing hydrogen into the kettle to react with the working solution until anthraquinone crystals are separated out, and stopping hydrogen feeding. Under the condition of isolating air, firstly separating out hydroanthraquinone crystals and a catalyst, then oxidizing and extracting the saturated hydrogenation solution, and measuring the hydrogenation efficiency.
The hydrogenation efficiency test can be carried out by a conventional method. For example: adding a proper amount of pure water and phosphoric acid into the hydrogenation solution, introducing pure oxygen at 50 ℃ for oxidation, and extracting the organic phase for multiple times by using the pure water after the color of the organic phase is changed from black to bright yellow. The aqueous phase was separated and collected, an appropriate amount of 20 wt% sulfuric acid was added, the hydrogen peroxide content was measured by titration with 0.03mol/L potassium permanganate, and the hydrogenation efficiency was calculated, the results are shown in table 4.
TABLE 4
The invention provides an alkyl anthraquinone composition and a preparation method thereof. The alkyl anthracene composition can be prepared by an anthracene alkylation reaction and separation process, and then oxidized to prepare the alkyl anthraquinone composition.
As can be seen from the results in tables 1 and 2, the alkyl anthracene composition provided by the present invention can prepare an alkyl anthracene composition with a specific structure and composition by controlling reaction and separation, and the obtained alkyl anthracene composition can be used for preparing an alkyl anthraquinone composition by an oxidation method, thereby providing a new idea for preparing a complex alkyl anthraquinone.
According to the method for separating anthracene and alkyl anthracene, the distillation solvent is introduced and the auxiliary distillation process is matched, so that anthracene is dissolved by the solvent and flows and is separated together with the anthracene, the problem of easy blockage in the process of separating anthracene is thoroughly solved, the high-efficiency separation of anthracene is realized, and the yield of anthracene is improved; aiming at the problems of high boiling point, easy condensation and high temperature coke formation of an alkyl anthracene mixture, the developed reduced pressure distillation process can realize one-step high-efficiency separation, directly obtain the alkyl anthracene composition, and has high product purity and separation yield and low separation difficulty.
As can be seen from the results of comparative example 2, the alkylanthraquinone composition provided by the present invention has better solubility properties and higher hydrogenation efficiency than the single anthraquinone.
The alkyl anthraquinone composition provided by the invention widens and enriches the types of anthraquinone carriers in the production of hydrogen peroxide, and brings a new direction for the industry.
The preparation method of the alkylanthraquinone composition provided by the invention is clean and efficient, has strong process flexibility, can be used for preparing a process in a targeted manner, and meets the requirements of different mixed alkylanthraquinone products.
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 (50)
1. An alkylanthraquinone composition comprising an alkyl substituent of anthraquinone having the formula C14+nH8+2nO2N is more than or equal to 2 and less than or equal to 6; the position of the alkyl substituent is alpha and/or beta to the anthraquinone ring.
2. The alkylanthraquinone composition of claim 1, wherein the alkyl substituent of said anthraquinone is represented by structural formula (1):
any three substituents are H, and the rest substituents are alkyl with the carbon atom number of 2-6; or,
any two substituents are H, the other two substituents are each independently an alkyl group having 2 to 4 carbon atoms, and the total number of carbon atoms is 6 or less.
3. The alkylanthraquinone composition of claim 2, wherein said alkylanthraquinone composition contains C16H12O2、C17H14O2、C18H16O2、C19H18O2And C20H20O2At least any two of the substances in (1).
4. The alkylanthraquinone composition of claim 3, wherein C is based on the total weight of said alkylanthraquinone composition16H12O2In an amount of 10-96 wt.%, C17H14O2In an amount of 0-10 wt.%, C18H16O2In an amount of 3.5 to 89.5 wt.%, C19H18O2In an amount of 0-30 wt.%, C20H20O2In an amount of 0.5 to 50 wt%;
preferably, with said alkyl anthraceneBased on the total weight of the quinone composition, C16H12O2In an amount of 30-80 wt.%, C17H14O2In an amount of 0-5 wt.%, C18H16O2In an amount of 15-65 wt.%, C19H18O2In an amount of 0-15 wt.%, C20H20O2In an amount of 5 to 30% by weight;
most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 35-55 wt.%, C17H14O2In an amount of 0-2 wt.%, C18H16O2In an amount of 25-50 wt.%, C19H18O2In an amount of 0-10 wt.%, C20H20O2Is contained in an amount of 10 to 25 wt%.
5. The alkylanthraquinone composition of claim 3, wherein C is based on the total weight of said alkylanthraquinone composition16H12O2In an amount of 0-10 wt.%, C17H14O2In an amount of 10 to 96.5 wt.%, C18H16O2In an amount of 0-30 wt.%, C19H18O2In an amount of 0-30 wt.%, C20H20O2The content of (B) is 3.5-90 wt%;
preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-5 wt.%, C17H14O2In an amount of 30-80 wt.%, C18H16O2In an amount of 0-15 wt.%, C19H18O2In an amount of 0-15 wt.%, C20H20O2The content of (A) is 15-70 wt%;
most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-2 wt.%, C17H14O2Of (1) containsIn an amount of 40-70 wt.%, C18H16O2In an amount of 0-15 wt.%, C19H18O2In an amount of 0-5 wt.%, C20H20O2Is contained in an amount of 15 to 45% by weight.
6. The alkylanthraquinone composition of claim 3, wherein C is based on the total weight of said alkylanthraquinone composition16H12O2In an amount of 0-10 wt.%, C17H14O2In an amount of 0-10 wt.%, C18H16O2In an amount of 10 to 99.1 wt.%, C19H18O2In an amount of 0.45-50 wt.%, C20H20O2The content of (B) is 0.45-30 wt%;
preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-5 wt.%, C17H14O2In an amount of 0-5 wt.%, C18H16O2In an amount of 40-95 wt.%, C19H18O2In an amount of 1-40 wt.%, C20H20O2In an amount of 1 to 25% by weight;
most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-2.5 wt.%, C17H14O2In an amount of 0-2.5 wt.%, C18H16O2In an amount of 70 to 90 wt.%, C19H18O2In an amount of 1-10 wt.%, C20H20O2Is contained in an amount of 1 to 15% by weight.
7. The alkylanthraquinone composition of claim 3, wherein C is based on the total weight of said alkylanthraquinone composition16H12O2In an amount of 0-10 wt.%, C17H14O2In an amount of 0-10 wt.%, C18H16O2In an amount of 0.5-50 wt.%, C19H18O2In an amount of 10 to 99 wt.%, C20H20O2The content of (B) is 0.5-30 wt%;
preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-5 wt.%, C17H14O2In an amount of 0-5 wt.%, C18H16O2In an amount of 1-40 wt.%, C19H18O2In an amount of 40-90 wt.%, C20H20O2In an amount of 1 to 20% by weight;
most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-2 wt.%, C17H14O2In an amount of 0-2 wt.%, C18H16O2In an amount of 1-40 wt.%, C19H18O2In an amount of 40-90 wt.%, C20H20O2Is contained in an amount of 1 to 20% by weight.
8. The alkylanthraquinone composition of claim 3, wherein C is based on the total weight of said alkylanthraquinone composition16H12O2In an amount of 0-10 wt.%, C17H14O2In an amount of 0-10 wt.%, C18H16O2In an amount of 0.5-50 wt.%, C19H18O2In an amount of 0.5-30 wt.%, C20H20O2In an amount of 10 to 99% by weight;
preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-5 wt.%, C17H14O2In an amount of 0-5 wt.%, C18H16O2In an amount of 1-40 wt.%, C19H18O2In an amount of 1-30 wt.%, C20H20O2In an amount of 40-95 wt%;
most preferably, C is based on the total weight of the alkylanthraquinone composition16H12O2In an amount of 0-2 wt.%, C17H14O2In an amount of 0-2 wt.%, C18H16O2In an amount of 15-40 wt.%, C19H18O2In an amount of 1-12 wt.%, C20H20O2Is present in an amount of 45 to 75 wt.%.
9. The alkylanthraquinone composition according to any one of claims 2 to 8, wherein,
C16H12O2is that a 9, 10-anthraquinone parent nucleus is connected with 1 ethyl;
C17H14O2is that 9, 10-anthraquinone mother nucleus is connected with 1 propyl;
C18H16O2the 9, 10-anthraquinone mother nucleus is connected with 1 butyl or 2 ethyl;
C19H18O2is 9, 10-anthraquinone mother nucleus linked to 1 pentyl group, or to 1 ethyl group and 1 propyl group;
C20H20O2is 9, 10-anthraquinone core linked to 1 hexyl group, or to 1 ethyl group and 1 butyl group, or to 2 propyl groups.
10. The alkylanthraquinone composition according to any one of claims 2 to 9, wherein the alkyl substituent is selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, tert-pentyl, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 2-dimethylbutyl, 3-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-ethylbutyl, One or more of 1-ethylbutyl, 1-dimethyl-2-methylpropyl, 1-methyl-2, 2-dimethylpropyl, 1-methyl-1-ethylpropyl, and 1-ethyl-2-methylpropyl;
preferably, the alkyl substituents are selected from one or more of ethyl, isopropyl, 1-methylpropyl, tert-butyl, 1-methylbutyl, tert-pentyl, 1-ethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1-ethylbutyl, 1-dimethyl-2-methylpropyl, 1-methyl-2, 2-dimethylpropyl, 1-methyl-1-ethylpropyl, 1-ethyl-2-methylpropyl.
11. A method of making an alkylanthraquinone composition, said method comprising:
contacting the alkyl anthracene composition with an oxidizing agent under oxidizing conditions and in the presence of an oxidizing reaction solvent and an oxidizing catalyst to effect an oxidation reaction to produce an alkyl anthracene oxidation product comprising an alkyl anthraquinone composition having an alkyl substituent of anthraquinone of formula C14+nH8+2nO2N is more than or equal to 2 and less than or equal to 6; the position of the alkyl substituent is alpha position and/or beta position of the anthraquinone ring;
wherein the alkyl anthracene composition contains an alkyl substituent of anthracene, and the molecular formula of the alkyl substituent of the anthracene is C14+nH10+2nN is more than or equal to 2 and less than or equal to 6; the position of the alkyl substituent is alpha and/or beta to the anthracycline.
12. The production method according to claim 11, wherein the production method of the alkyl anthracene composition includes: contacting anthracene with an alkylating agent under alkylation conditions and in the presence of an alkylation reaction solvent and an alkylation catalyst to carry out alkylation reaction to obtain an anthracene alkylation reaction product containing an alkyl anthracene system, wherein the alkyl anthracene system contains an alkyl anthracene composition;
preferably, the anthracene is contacted with the alkylating agent in a manner that: the raw material liquid containing anthracene, alkylation catalyst and alkylation reaction solvent is contacted with alkylation reagent to make alkylation reaction.
13. The production method according to claim 11 or 12, wherein the molar ratio of anthracene to the alkylating agent is 0.05:1 to 20:1, preferably 0.1:1 to 5: 1.
14. The production method according to claim 11 or 12, wherein the alkylating agent is one or more of alkylating agents containing 2 to 6 carbon atoms;
preferably, the alkylating agent is one or more of olefin, alcohol, halogenated hydrocarbon and ether substances containing 2-6 carbon atoms;
more preferably, the alkylating agent is one or more of a mono-olefin containing 2 to 6 carbon atoms, a mono-alcohol and a mono-halohydrocarbon;
more preferably, the alkylating agent is a mono-olefin having from 2 to 6 carbon atoms.
15. The production method according to claim 11 or 12, wherein the alkylation reaction solvent is a solvent having a dielectric constant of 1 to 10 at 20 ℃, and the alkylation reaction solvent is C6And above, preferably C6-C12One or more of paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted, preferably one or more of monobasic, dibasic or polybasic substitutes of benzene; more preferably one or more of benzene multi-substituted compounds, the substituent is C1-C4One or more of alkyl and halogen elements of (a); further preferably, the alkylation reaction solvent is one or more of polyalkyl substitutes of benzene; most preferably, the alkylation reaction solvent is selected from one or more of 1,2, 3-trimethylbenzene, 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene and 1,2,3, 4-tetramethylbenzene;
the content of anthracene is 5 to 60 wt%, preferably 8 to 50 wt%, based on the total weight of anthracene and the alkylation reaction solvent.
16. The production method according to claim 11 or 12, wherein the alkylation catalyst is selected from one or more of kaolin, bentonite, montmorillonite, zeolite, X molecular sieve, Y molecular sieve, β molecular sieve, MCM-41, SBA-15, cation exchange resin, perfluorosulfonic acid resin, immobilized sulfuric acid, immobilized sulfonic acid, immobilized phosphoric acid, silica-alumina composite oxide, sulfuric acid, perchloric acid, tetrafluoroboric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, boron trifluoride, aluminum trichloride, and zinc dichloride; further preferably selected from one or more of zeolite, Y molecular sieve, MCM-41, SBA-15, perfluorosulfonic acid resin, immobilized sulfonic acid, silicon-aluminum composite oxide, sulfuric acid, tetrafluoroboric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid;
the content of the alkylation catalyst is 0.01 to 50% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, based on the total weight of the raw material liquid containing anthracene, the alkylation catalyst and the alkylation reaction solvent.
17. The production method according to claim 11 or 12, wherein the alkylation reaction conditions include: the reaction temperature is 80-250 ℃, preferably 90-200 ℃; the reaction pressure is 0-2MPa, preferably 0-1 MPa; the reaction time is 0.01-48h, preferably 0.5-24 h.
18. The production method according to claim 11, wherein the alkyl anthracene composition contains an alkyl substituent of anthracene represented by structural formula (2):
any three substituents are H, and the rest substituents are alkyl with the carbon atom number of 2-6; or,
any two substituents are H, the other two substituents are each independently an alkyl group having 2 to 4 carbon atoms, and the total number of carbon atoms is 6 or less.
19. The production method according to claim 18, wherein the alkyl anthracene composition contains C16H14、C17H16、C18H18、C19H20And C20H22At least any two of them.
20. The production method according to claim 19,
contacting anthracene with an alkylating reagent containing 2 carbon atoms for alkylation reaction to obtain an anthracene alkylation reaction product, wherein:
based on the total weight of the alkyl anthracene composition, C16H14In an amount of 10-95 wt.%, C17H16In an amount of 0-10 wt.%, C18H18In an amount of 4-89 wt.%, C19H20In an amount of 0-30 wt.%, C20H22In an amount of 1 to 50% by weight; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 30-80 wt.%, C17H16In an amount of 0-5 wt.%, C18H18In an amount of 15-65 wt.%, C19H20In an amount of 0-15 wt.%, C20H22In an amount of 5 to 30% by weight; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 35-55 wt.%, C17H16In an amount of 0-2 wt.%, C18H18In an amount of 25-50 wt.%, C19H20In an amount of 0-10 wt.%, C20H22Is contained in an amount of 10 to 25 wt%.
21. The production method according to claim 19,
contacting anthracene with an alkylating reagent containing 3 carbon atoms for alkylation reaction to obtain an anthracene alkylation reaction product, wherein:
based on the total weight of the alkyl anthracene composition, C16H14In an amount of 0-10 wt.%, C17H16In an amount of 10-96 wt.%, C18H18In an amount of 0-30 wt.%, C19H20In an amount of 0-30 wt.%, C20H22The content of (A) is 4-90 wt%; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-5 wt.%, C17H16In an amount of 30-80 wt.%, C18H18In an amount of 0-15 wt.%, C19H20In an amount of 0-15 wt.%, C20H22The content of (A) is 15-70 wt%; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-2 wt.%, C17H16In an amount of 40-70 wt.%, C18H18In an amount of 0-15 wt.%, C19H20In an amount of 0-5 wt.%, C20H22Is contained in an amount of 15 to 45% by weight.
22. The production method according to claim 19,
contacting anthracene with an alkylating reagent containing 4 carbon atoms for alkylation reaction to obtain an anthracene alkylation reaction product, wherein:
based on the total weight of the alkyl anthracene composition, C16H14In an amount of 0-10 wt.%, C17H16In an amount of 0-10 wt.%, C18H18In an amount of 10 to 99 wt.%, C19H20In an amount of 0.5-50 wt.%, C20H22The content of (B) is 0.5-30 wt%; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-5 wt.%, C17H16In an amount of 0-5 wt.%, C18H18In an amount of 40-95 wt.%, C19H20In an amount of 1-40 wt.%, C20H22In an amount of 1 to 25% by weight; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-2.5 wt.%, C17H16In an amount of0 to 2.5% by weight, C18H18In an amount of 70 to 90 wt.%, C19H20In an amount of 1-10 wt.%, C20H22Is contained in an amount of 1 to 15% by weight.
23. The production method according to claim 19,
contacting anthracene with an alkylating reagent containing 5 carbon atoms for alkylation reaction to obtain an anthracene alkylation reaction product, wherein:
based on the total weight of the alkyl anthracene composition, C16H14In an amount of 0-10 wt.%, C17H16In an amount of 0-10 wt.%, C18H18In an amount of 0.5-50 wt.%, C19H20In an amount of 10 to 99 wt.%, C20H22The content of (B) is 0.5-30 wt%; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-5 wt.%, C17H16In an amount of 0-5 wt.%, C18H18In an amount of 1-40 wt.%, C19H20In an amount of 40-90 wt.%, C20H22In an amount of 1 to 20% by weight; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-2 wt.%, C17H16In an amount of 0-2 wt.%, C18H18In an amount of 1-40 wt.%, C19H20In an amount of 40-90 wt.%, C20H22Is contained in an amount of 1 to 20% by weight.
24. The production method according to claim 19,
contacting anthracene with an alkylating reagent containing 6 carbon atoms for alkylation reaction to obtain an anthracene alkylation reaction product, wherein:
based on the total weight of the alkyl anthracene composition, C16H14In an amount of 0-10 wt.%, C17H16In an amount of 0-10 wt.%, C18H18The content of (B) is 0.5-50 wt%，C19H20In an amount of 0.5-30 wt.%, C20H22In an amount of 10 to 99% by weight; preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-5 wt.%, C17H16In an amount of 0-5 wt.%, C18H18In an amount of 1-40 wt.%, C19H20In an amount of 1-30 wt.%, C20H22In an amount of 40-95 wt.%; most preferably, C is based on the total weight of the alkyl anthracene composition16H14In an amount of 0-2 wt.%, C17H16In an amount of 0-2 wt.%, C18H18In an amount of 15-40 wt.%, C19H20In an amount of 1-12 wt.%, C20H22Is present in an amount of 45 to 75 wt.%.
25. The production method according to any one of claims 18 to 24,
C16H14an anthracycline is attached to 1 ethyl group;
C17H16is an anthracycline linked to 1 propyl group;
C18H18is an anthracycline linked to 1 butyl group, or to 2 ethyl groups;
C19H20is an anthracycline with 1 pentyl group attached, or with 1 ethyl group and 1 propyl group attached;
C20H22the anthracycline is linked to 1 hexyl group, or to 1 ethyl group and 1 butyl group, or to 2 propyl groups.
26. The method according to any one of claims 18 to 25, wherein the alkyl substituent is selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, tert-pentyl, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 2-dimethylbutyl, 3-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-ethylbutyl, and the like, One or more of 1-ethylbutyl, 1-dimethyl-2-methylpropyl, 1-methyl-2, 2-dimethylpropyl, 1-methyl-1-ethylpropyl, and 1-ethyl-2-methylpropyl;
preferably, the alkyl substituent is selected from one or more of ethyl, isopropyl, 1-methylpropyl, tert-butyl, 1-methylbutyl, tert-pentyl, 1-ethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1-ethylbutyl, 1-dimethyl-2-methylpropyl, 1-methyl-2, 2-dimethylpropyl, 1-methyl-1-ethylpropyl and 1-ethyl-2-methylpropyl.
27. The production process according to any one of claims 11 to 26, wherein the alkylation reaction product contains a light component having a boiling point lower than that of anthracene, optionally anthracene, and an alkyl anthracene system containing the alkyl anthracene composition, the process further comprising separating the alkyl anthracene composition from the anthracene alkylation reaction product;
mode 1:
in the mixture of the alkylation reaction product with the boiling point being more than or equal to that of anthracene, the content of anthracene is less than or equal to 1 weight percent;
the separation method comprises the following steps:
pre-separation: separating light components with boiling points lower than that of anthracene to obtain an alkyl anthracene system;
separation of alkyl anthracene composition: separating the alkyl anthracene composition C from the alkyl anthracene system by distillation14+nH10+2nN is more than or equal to 2 and less than or equal to 6; or,
mode 2:
the content of anthracene in a mixture with a boiling point of more than or equal to that of anthracene in the alkylation reaction product is more than or equal to 10 wt%;
the separation method comprises the following steps:
pre-separation: separating light components with boiling points lower than that of anthracene to obtain a mixture containing anthracene and an alkyl anthracene system;
and (3) distilling the solvent to assist in separating anthracene: distilling a mixture containing anthracene and an alkyl anthracene system in the presence of a distillation solvent, and collecting the alkyl anthracene system, wherein the distillation solvent is an organic solvent which can dissolve anthracene and has a boiling point of between 100 ℃ and 340 ℃ in the process of auxiliary separation of anthracene;
separation of alkyl anthracene composition: separating the alkyl anthracene composition C from the alkyl anthracene system by distillation14+nH10+2n，2≤n≤6；
In the mixture of the alkylation reaction product with the boiling point being more than or equal to that of anthracene, the content of anthracene is more than 1 wt% and less than 10 wt%, and adopting any one separation mode of a mode 1 or a mode 2, preferably, in the mixture of the alkylation reaction product with the boiling point being more than or equal to that of anthracene, the content of anthracene is less than or equal to 5 wt%, and adopting the separation mode of the mode 1; in the mixture of the alkylation reaction product with the boiling point more than or equal to that of anthracene, the content of anthracene is more than 5 wt%, and the separation mode of the mode 2 is adopted.
28. The production method according to claim 27, wherein, in the separation step of the alkyl anthracene composition according to mode 1, distillation conditions under which the alkyl anthracene composition is separated from the alkyl anthracene system by 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 200-;
preferably, the pressure at the top of the column is from 0.05 to 10kpa, the temperature at the bottom of the column is from 210 ℃ to 340 ℃, 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.
29. The method according to claim 27, wherein in the mode 2, in the step of distilling the solvent to assist in separating anthracene, the distilled solvent is an organic solvent with a boiling point of 200-340 ℃, and is preferably selected from C12-C19One or more of linear and/or branched alkanes of (a), halogenated hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters and ethers;
more preferably, the alkane is C12-C17One or more of a linear alkane and/or a branched alkane of (a);
more preferably, the halogenated hydrocarbon is selected from trichlorobenzene, tetrachlorobenzene, tribromobenzene, tetrabromobenzene, chlorinated C10-C18Alkane and bromo C10-C18One or more of an alkane;
more preferably, the aromatic hydrocarbon is an alkyl substituent of benzene, and the total carbon number of the substituted alkyl is 4-12; further preferably one or more of butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene, dodecylbenzene, triethylbenzene, tetraethylbenzene, dipropylbenzene, tripropylbenzene, dibutylbenzene, and dipentylbenzene;
more preferably, the arene alkane is a benzene substitute, and is further preferably one or more of diphenylmethane and an alkyl substitute thereof, and diphenylethane and an alkyl substitute thereof; more preferably one or more of diphenylmethane, methyldiphenylmethane and 1, 2-diphenylethane;
more preferably, the arene alkane is naphthalene and/or alkyl substituent of the naphthalene, and the total carbon number of the substituted alkyl of the naphthalene is 1-4; further preferably one or more of naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, diethylnaphthalene, propylnaphthalene, methylethylnaphthalene and butylnaphthalene;
more preferably, the alcohol is selected from one or more of benzyl alcohol, glycerol, diethylene glycol, triethylene glycol and tetraethylene glycol;
more preferably, the ketone is selected from one or more of 1,1, 3-trimethylcyclohexenone, N-methylpyrrolidone and 1, 3-dimethyl-2-imidazolidinone;
more preferably, the ester is selected from one or more of the group consisting of a dicarboxylic acid ester, ethyl benzoate, dimethyl phthalate, dibutyl phthalate, ethylene glycol carbonate, propylene glycol carbonate and trioctyl phosphate;
more preferably, the ether is selected from one or more of ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diphenyl ether and sulfolane.
30. The production method according to claim 27 or 29, wherein the conditions for distilling the solvent-assisted separation of anthracene in mode 2 include:
the pressure at the top of the distillation tower is 0.5-40kpa, the temperature at the bottom of the distillation tower is 200-;
preferably, the pressure at the top of the distillation tower is 1-20kpa, the temperature at the bottom of the distillation tower is 230-350 ℃, the number of theoretical plates is 16-50, the mass ratio of the distillation solvent to the anthracene is 1:1-15:1, and the reflux ratio at the top of the distillation tower is 0.2-1.
31. The production method according to claim 27, wherein, in the separation step of the alkyl anthracene composition according to mode 2, distillation conditions under which the alkyl anthracene composition is separated from the alkyl anthracene system by 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 200-;
preferably, the pressure at the top of the tower is 0.05-10kpa, 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.
32. The production method according to claim 27 or 29, wherein the step of distilling the solvent-assisted separation of anthracene further comprises: collecting a mixture containing anthracene and a distillation solvent, and separating anthracene from the distillation solvent by one or more separation methods selected from extraction, crystallization, and distillation, preferably distillation.
33. The method of claim 27, wherein in the mode 1 or 2, the pre-separation method comprises: distilling a mixture containing a light component having a boiling point lower than that of anthracene, optionally containing anthracene, and an alkyl anthracene system containing an alkyl anthracene composition to obtain a distillate containing a light component having a boiling point lower than that of anthracene, and a bottoms product containing optionally containing anthracene and an alkyl anthracene system, under conditions comprising: the distillation temperature is 50-350 deg.C, preferably 60-300 deg.C, and the distillation pressure is 0.1-20kpa, preferably 0.5-15 kpa.
34. The production method according to any one of claims 27 to 33, wherein the light component having a boiling point lower than that of anthracene contains a reaction solvent for producing an alkyl anthracene system by alkylation of anthracene, an alkylating agent, and a by-product produced by the alkylation;
the anthracene alkylation product also contains an alkylation catalyst for preparing an alkyl anthracene system from anthracene by alkylation, and the preparation method further comprises separating the alkylation catalyst before the pre-separation in the mode 1 or the mode 2.
35. The method according to claim 11, wherein the alkyl substituent of the anthraquinone is represented by the structural formula (1):
any three substituents are H, and the rest substituents are alkyl with the carbon atom number of 2-6; or,
any two substituents are H, the other two substituents are each independently an alkyl group having 2 to 4 carbon atoms, and the total number of carbon atoms is 6 or less.
36. The production method according to any one of claims 11 to 35, wherein the alkyl anthracene composition is contacted with the oxidizing agent by: and (3) separating the alkyl anthracene composition from the anthracene alkylation reaction product, and contacting the mixture of the separated alkyl anthracene composition, the oxidation catalyst and the oxidation reaction solvent with an oxidant for oxidation reaction to obtain the alkyl anthraquinone composition.
37. The production method according to claim 36, wherein the oxidizing agent is hydrogen peroxide, preferably the hydrogen peroxide is used in the form of an aqueous hydrogen peroxide solution; the molar ratio of the oxidant to the sum of all species having an anthracycline structure in the separated alkyl anthracene composition is from 0.01:1 to 100:1, more preferably from 1:1 to 50: 1;
the oxidation catalyst is selected from one or more of oxides of alkaline earth metals, hydroxides of alkaline earth metals, oxygen-containing compounds of transition metals and oxygen-containing compounds of lanthanide metals, preferably the catalyst is selected from one or more of group IIA, group IVB, group VB, group VIB, group VIIB, group VIII metals and oxygen-containing compounds of lanthanide metals, more preferably the catalyst is selected from one or more 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 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, cobalt oxide, manganese dioxide, manganese, One or more of nickel oxide, nickel sesquioxide, lanthanum nitrate, lanthanum sesquioxide and cerium dioxide; the molar ratio of the oxidant to the oxidation catalyst is 0.01:1 to 100:1, preferably 0.1:1 to 30: 1;
preferably, the oxidant hydrogen peroxide is used in combination with a catalyst selected from one or more of oxides of alkaline earth metals, hydroxides of alkaline earth metals, oxygen-containing compounds of transition metals and oxygen-containing compounds of lanthanide metals.
38. The production method according to claim 36, wherein the oxidation reaction solvent is a solvent having a dielectric constant of 1 to 50 at 20 ℃, and the oxidation reaction solvent is C6And above, preferably C6-C12One or more of paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted, preferably one or more of monobasic, dibasic or polybasic substitutes of benzene; more preferably one or more of benzene multi-substituted compounds, the substituent is C1-C4One or more of alkyl and halogen elements of (a); more preferably, the oxidation reaction solvent is one or more of polyalkyl substituents of benzene; more preferably, the oxidation reaction solvent is selected from one or more of 1,2, 3-trimethylbenzene, 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene and 1,2,3, 4-tetramethylbenzene; more preferably, the oxidation reaction solvent is carbon number1-4 of one or more of aliphatic alcohol, tetrahydrofuran, acetone, ethyl acetate, acetonitrile, dimethyl sulfoxide, sulfolane, N-dimethylaniline, formamide, acetamide, N-alkyl substituted amide and N-alkyl pyrrolidone, wherein the number of alkyl substituents is 1-2, and each alkyl substituent is independently C1-C4Alkyl groups of (a); most preferably, the oxidation reaction solvent is selected from one or more of methanol, t-butanol, acetone, dimethyl sulfoxide, sulfolane, N-dimethylaniline, formamide, acetamide, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-methylpyrrolidone, and N-ethylpyrrolidone;
the content of the separated alkyl anthracene composition is 0.1 to 80% by weight, preferably 5 to 50% by weight, based on the total weight of the separated alkyl anthracene composition and the oxidation reaction solvent.
39. The production method according to any one of claims 11 to 26 and 35, wherein the alkyl anthracene composition is contacted with the oxidizing agent by: contacting a mixture of an anthracene alkylation reaction product containing the alkyl anthracene composition, an oxidation catalyst, and optionally an oxidation reaction solvent, with an oxidizing agent for oxidation to produce an alkyl anthracene oxidation product containing the alkyl anthraquinone composition, and separating the alkyl anthraquinone composition from the alkyl anthracene oxidation product;
preferably:
mode 1C: the alkylation reaction solvent used in the anthracene alkylation reaction is the same as the oxidation reaction solvent used in the alkyl anthracene oxidation reaction, the alkylation catalyst in the anthracene alkylation reaction product is separated to obtain an alkylation product mixture containing a light component with a boiling point lower than that of anthracene, optionally contained anthracene, and an alkyl anthracene system containing the alkyl anthracene composition, and the mixture of the alkylation product mixture and the oxidation catalyst is contacted with an oxidizing agent to carry out an oxidation reaction to obtain an alkyl anthracene oxidation product containing the alkyl anthraquinone composition; or,
mode 2C: the alkylation reaction solvent used in the anthracene alkylation reaction is different from the oxidation reaction solvent used in the alkyl anthracene oxidation reaction, the alkylation catalyst and the alkylation reaction solvent in the anthracene alkylation reaction product are separated, so that an alkylation product mixture containing anthracene and an alkyl anthracene system with a boiling point lower than that of anthracene is obtained, the anthracene selectively contained in the anthracene and the alkyl anthracene system contains the alkyl anthracene composition, and the mixture of the alkylation product mixture, the oxidation catalyst and the oxidation reaction solvent is contacted with an oxidizing agent for oxidation reaction to obtain an alkyl anthracene oxidation product containing the alkyl anthraquinone composition.
40. The production method according to claim 39, wherein the alkylanthracene oxidation product contains a substance having a boiling point lower than that of anthraquinone and optionally anthraquinone and alkylanthraquinone systems, the alkylanthraquinone system containing the alkylanthraquinone composition, and the method for separating the alkylanthraquinone composition from the alkylanthracene oxidation product comprises:
mode 3:
the content of anthraquinone in the mixture of alkyl anthracene oxidation products with the boiling point being more than or equal to that of anthraquinone is less than or equal to 1 wt%;
the separation method comprises the following steps:
pre-separation: separating the substances with the boiling points lower than that of the anthraquinone to obtain an alkyl anthraquinone system;
isolation of the alkylanthraquinone composition: separating the said alkylanthraquinone composition C from the alkylanthraquinone system by distillation14+ nH8+2nO2，2≤n≤6；
Mode 4:
the content of anthraquinone in the mixture of the alkyl anthracene oxidation product with the boiling point more than or equal to anthraquinone is more than or equal to 10 weight percent;
the separation method comprises the following steps:
pre-separation: separating the substances with the boiling point lower than that of the anthraquinone to obtain a mixture containing the anthraquinone and the alkyl anthraquinone systems;
anthraquinone separation: the method for separating the anthraquinone is selected from one or more of extraction separation, melting crystallization separation of the anthraquinone, solvent crystallization separation of the anthraquinone and distillation separation of the anthraquinone, preferably distillation separation of the anthraquinone, and further preferably distillation solvent auxiliary separation of the anthraquinone: distilling a mixture containing anthraquinone and an alkylanthraquinone system in the presence of a distillation solvent, and collecting the alkylanthraquinone system, wherein the distillation solvent is an organic solvent which can dissolve the anthraquinone and has a boiling point of between 100 ℃ and 340 ℃ in the process of assisting in separating the anthraquinone;
isolation of the alkylanthraquinone composition: separation of the alkylanthraquinone composition C from the alkylanthraquinone System by distillation14+nH8+ 2nO2，2≤n≤6。
In the mixture of the alkyl anthracene oxidation product with the boiling point being more than or equal to that of anthraquinone, the content of anthraquinone is more than 1 wt% and less than 10 wt%, adopting any one separation mode of a mode 3 or a mode 4, preferably, in the mixture of the alkyl anthracene oxidation product with the boiling point being more than or equal to that of anthraquinone, the content of anthraquinone is less than or equal to 5 wt%, adopting the separation mode of the mode 3; in the mixture of alkyl anthracene oxidation product with boiling point not less than that of anthraquinone, the content of anthraquinone is higher than 5 wt%, and the separation mode of mode 4 is adopted.
41. The production method according to claim 40, wherein in the mode 3, in the step of separating the alkylanthraquinone composition, the alkylanthraquinone composition C is separated from the alkylanthraquinone system by distillation14+nH8+2nO2And n is more than or equal to 2 and less than or equal to 6, and the 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 230-;
preferably, the pressure at the top of the column is from 0.05 to 10kpa, the temperature at the bottom of the column is from 240 ℃ to 370 ℃, 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.
42. The method as claimed in claim 40, wherein in the mode 4, the distillation solvent is an organic solvent with a boiling point of 200-340 ℃, preferably selected from C12-C19One or more of linear and/or branched alkanes, halogenated hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters and ethers of (A)A plurality of types;
more preferably, the alkane is C12-C17One or more of a linear alkane and/or a branched alkane of (a);
more preferably, the halogenated hydrocarbon is selected from trichlorobenzene, tetrachlorobenzene, tribromobenzene, tetrabromobenzene, chlorinated C10-C18Alkane and bromo C10-C18One or more of an alkane;
more preferably, the aromatic hydrocarbon is an alkyl substituent of benzene, and the total carbon number of the substituted alkyl is 4-12; further preferably one or more of butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene, dodecylbenzene, triethylbenzene, tetraethylbenzene, dipropylbenzene, tripropylbenzene, dibutylbenzene, and dipentylbenzene;
more preferably, the arene alkyl is a benzene substituent, and further preferably one or more of diphenylmethane and an alkyl substituent thereof, and diphenylethane and an alkyl substituent thereof; more preferably one or more of diphenylmethane, methyldiphenylmethane and 1, 2-diphenylethane;
more preferably, the arene alkane is naphthalene and/or alkyl substituent of the naphthalene, and the total carbon number of the substituted alkyl of the naphthalene is 1-4; further preferably one or more of naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, diethylnaphthalene, propylnaphthalene, methylethylnaphthalene and butylnaphthalene;
more preferably, the alcohol is selected from one or more of benzyl alcohol, glycerol, diethylene glycol, triethylene glycol and tetraethylene glycol;
more preferably, the ketone is selected from one or more of 1,1, 3-trimethylcyclohexenone, N-methylpyrrolidone and 1, 3-dimethyl-2-imidazolidinone;
more preferably, the ester is selected from one or more of the group consisting of a dicarboxylic acid ester, ethyl benzoate, dimethyl phthalate, dibutyl phthalate, ethylene glycol carbonate, propylene glycol carbonate and trioctyl phosphate;
more preferably, the ether is selected from one or more of ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diphenyl ether and sulfolane.
43. The production process according to claim 40 or 42, wherein the conditions for distilling the solvent-assisted separation of the anthraquinones in mode 4 include:
the pressure at the top of the distillation tower is 0.5-40kpa, the temperature at the bottom of the distillation tower is 230-430 ℃, the number of theoretical plates is 12-55, the mass ratio of the distillation solvent to the anthraquinone is 0.1:1-30:1, and the reflux ratio at the top of the distillation tower is 0.1-4;
preferably, the pressure at the top of the distillation tower is 1-20kpa, the temperature at the bottom of the distillation tower is 260-380 ℃, the number of theoretical plates is 16-50, the mass ratio of the distillation solvent to the anthraquinone is 1:1-15:1, and the reflux ratio at the top of the distillation tower is 0.2-1.
44. The production method according to claim 40 or 42, wherein the distillation of the solvent-assisted separation of anthraquinones further comprises: collecting a mixture containing the anthraquinones and the distilled solvent, and separating the anthraquinones from the distilled solvent by one or more separation methods selected from the group consisting of extraction, crystallization and distillation.
45. The production method according to claim 40, wherein in the mode 4, in the step of separating the alkylanthraquinone composition, the alkylanthraquinone composition C is separated from the alkylanthraquinone system by distillation14+nH8+2nO2And n is more than or equal to 2 and less than or equal to 6, and the 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 230-;
preferably, the pressure at the top of the column is from 0.05 to 10kpa, the temperature at the bottom of the column is from 240 ℃ to 370 ℃, 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.
46. The method of any one of claims 40 to 45, wherein in mode 3 or mode 4, the method of pre-separating comprises: distilling a mixture containing substances with the boiling point lower than that of anthraquinone, selectively containing anthraquinone and a system containing alkylanthraquinone to obtain a distillate containing substances with the boiling point lower than that of anthraquinone and a bottom product containing selectively containing anthraquinone and alkylanthraquinone systems, wherein the distillation conditions comprise: the distillation temperature is 50-390 ℃, preferably 60-340 ℃, and the distillation pressure is 0.1-20kpa, preferably 0.5-15 kpa.
47. The production method according to any one of claims 40 to 46, wherein the substance having a boiling point lower than that of anthraquinone contains an oxidation reaction solvent and an oxidizing agent and an oxidation reaction by-product;
the oxidation product of alkylanthraquinone also contains an oxidation catalyst for preparing alkylanthraquinone system by oxidation of alkylanthraquinone, and the preparation method further comprises separating the oxidation catalyst before the preliminary separation in the mode 3 or the mode 4.
48. The production method according to claim 39, wherein the oxidizing agent is hydrogen peroxide; preferably, the hydrogen peroxide is used in the form of an aqueous hydrogen peroxide solution; the molar ratio of oxidant to the sum of all substances having an anthracycline structure in the alkylation product mixture is from 0.01:1 to 100:1, more preferably from 1:1 to 50: 1;
the oxidation catalyst is selected from one or more of oxides of alkaline earth metals, hydroxides of alkaline earth metals, oxygen-containing compounds of transition metals and oxygen-containing compounds of lanthanide metals, preferably the catalyst is selected from one or more of group IIA, group IVB, group VB, group VIB, group VIIB, group VIII metals and oxygen-containing compounds of lanthanide metals, more preferably the catalyst is selected from one or more 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 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, cobalt oxide, manganese dioxide, manganese, One or more of nickel oxide, nickel sesquioxide, lanthanum nitrate, lanthanum sesquioxide and cerium dioxide; the molar ratio of the oxidant to the oxidation catalyst is 0.01:1 to 100:1, preferably 0.1:1 to 30: 1;
preferably, the oxidant hydrogen peroxide is used in combination with a catalyst selected from one or more of oxides of alkaline earth metals, hydroxides of alkaline earth metals, oxygen-containing compounds of transition metals and oxygen-containing compounds of lanthanide metals.
49. The production method according to claim 39, wherein the oxidation reaction solvent is a solvent having a dielectric constant of 1 to 50 at 20 ℃ and C6And above, preferably C6-C12One or more of paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted, preferably one or more of monobasic, dibasic or polybasic substitutes of benzene; more preferably one or more of benzene multi-substituted compounds, the substituent is C1-C4One or more of alkyl and halogen elements of (a); more preferably, the oxidation reaction solvent is one or more of polyalkyl substituents of benzene; more preferably, the oxidation reaction solvent is one or more selected from the group consisting of 1,2, 3-trimethylbenzene, 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, and 1,2,3, 4-tetramethylbenzene; more preferably, the oxidation reaction solvent is one or more of aliphatic alcohol having 1 to 4 carbon atoms, tetrahydrofuran, acetone, ethyl acetate, acetonitrile, dimethyl sulfoxide, sulfolane, N-dimethylaniline, formamide, acetamide, N-alkyl substituted amide and N-alkyl pyrrolidone, wherein the number of alkyl substituents is 1 to 2, and each alkyl substituent is independently C1-C4Alkyl groups of (a); most preferably, the oxidation reaction solvent is selected from one or more of methanol, t-butanol, acetone, dimethyl sulfoxide, sulfolane, N-dimethylaniline, formamide, acetamide, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-methylpyrrolidone, and N-ethylpyrrolidone;
the content of the alkylation reaction product mixture is from 0.1 to 80% by weight, preferably from 5 to 50% by weight, based on the total weight of the alkylation product mixture and the oxidation reaction solvent.
50. The production method according to any one of claims 11 and 36 to 49, wherein the conditions of the oxidation reaction include: the reaction temperature is 10-200 ℃, and preferably 20-120 ℃; the reaction pressure is 0-1MPa, preferably 0-0.5 MPa; the reaction time is 0.01-48h, preferably 0.5-24 h.
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