CN109467056A - Peroxidating method for preparing hydrogen - Google Patents
Peroxidating method for preparing hydrogen Download PDFInfo
- Publication number
- CN109467056A CN109467056A CN201811036580.4A CN201811036580A CN109467056A CN 109467056 A CN109467056 A CN 109467056A CN 201811036580 A CN201811036580 A CN 201811036580A CN 109467056 A CN109467056 A CN 109467056A
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- CN
- China
- Prior art keywords
- solution
- reproduction operation
- hydrogen peroxide
- working solution
- distillation
- Prior art date
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- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 139
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 240
- 239000000243 solution Substances 0.000 claims abstract description 191
- 238000004821 distillation Methods 0.000 claims abstract description 139
- 239000012224 working solution Substances 0.000 claims abstract description 134
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 118
- 238000004519 manufacturing process Methods 0.000 claims abstract description 72
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 70
- 239000003513 alkali Substances 0.000 claims abstract description 48
- 238000004140 cleaning Methods 0.000 claims abstract description 40
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 39
- 230000008929 regeneration Effects 0.000 claims abstract description 33
- 238000011069 regeneration method Methods 0.000 claims abstract description 33
- 238000011084 recovery Methods 0.000 claims abstract description 25
- 239000006227 byproduct Substances 0.000 claims abstract description 23
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 238000002360 preparation method Methods 0.000 claims description 52
- 238000001953 recrystallisation Methods 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 48
- 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 description 25
- 238000000605 extraction Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 24
- -1 alkyl tetrahydro anthraquinone Chemical compound 0.000 claims description 22
- 239000004615 ingredient Substances 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 22
- 239000002798 polar solvent Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- OTBHDFWQZHPNPU-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CCCC2 OTBHDFWQZHPNPU-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- RKMPHYRYSONWOL-UHFFFAOYSA-N 1-ethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(CC)CCC2 RKMPHYRYSONWOL-UHFFFAOYSA-N 0.000 description 5
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical class C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IMXBRVLCKXGWSS-UHFFFAOYSA-N methyl 2-cyclohexylacetate Chemical compound COC(=O)CC1CCCCC1 IMXBRVLCKXGWSS-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- AXHRXVXCOMMNLG-UHFFFAOYSA-N 1-hydroxy-10h-anthracen-9-one Chemical compound C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O AXHRXVXCOMMNLG-UHFFFAOYSA-N 0.000 description 2
- LZNGSHFBWBKBFH-UHFFFAOYSA-N 1-pentyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(CCCCC)CCC2 LZNGSHFBWBKBFH-UHFFFAOYSA-N 0.000 description 2
- INPHIYULSHLAHR-UHFFFAOYSA-N 1-pentylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCCC INPHIYULSHLAHR-UHFFFAOYSA-N 0.000 description 2
- JORLUGVBYJSSAW-UHFFFAOYSA-N 2-ethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(CC)CC2 JORLUGVBYJSSAW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- MMBMIVSDYYPRHH-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO.OO MMBMIVSDYYPRHH-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- UJJXSZLNJPOPBB-UHFFFAOYSA-N 1,2,3,4-tetrahydroxy-10h-anthracen-9-one Chemical compound C1=CC=C2CC3=C(O)C(O)=C(O)C(O)=C3C(=O)C2=C1 UJJXSZLNJPOPBB-UHFFFAOYSA-N 0.000 description 1
- GNRPVZNNVOGXHD-UHFFFAOYSA-N 1,2-dimethylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(C)C(C)=CC=C3C(=O)C2=C1 GNRPVZNNVOGXHD-UHFFFAOYSA-N 0.000 description 1
- UAGHCYPWINAKSA-UHFFFAOYSA-N 1,3-dimethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(C)CC2C UAGHCYPWINAKSA-UHFFFAOYSA-N 0.000 description 1
- YPGZWANKCCQIBY-UHFFFAOYSA-N 1,3-dimethylanthracene Chemical compound C1=CC=CC2=CC3=CC(C)=CC(C)=C3C=C21 YPGZWANKCCQIBY-UHFFFAOYSA-N 0.000 description 1
- VYFTZEZPCGUQOG-UHFFFAOYSA-N 1,4-dimethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(C)CCC2C VYFTZEZPCGUQOG-UHFFFAOYSA-N 0.000 description 1
- DVFAVJDEPNXAME-UHFFFAOYSA-N 1,4-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(C)=CC=C2C DVFAVJDEPNXAME-UHFFFAOYSA-N 0.000 description 1
- MUVQKFGNPGZBII-UHFFFAOYSA-N 1-anthrol Chemical compound C1=CC=C2C=C3C(O)=CC=CC3=CC2=C1 MUVQKFGNPGZBII-UHFFFAOYSA-N 0.000 description 1
- NJMCYPCKTIZMIZ-UHFFFAOYSA-N 1-butyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(CCCC)CCC2 NJMCYPCKTIZMIZ-UHFFFAOYSA-N 0.000 description 1
- BVEIKFLZWBDLJG-UHFFFAOYSA-N 1-butylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCC BVEIKFLZWBDLJG-UHFFFAOYSA-N 0.000 description 1
- JQLVCHDTPJYDIN-UHFFFAOYSA-N 1-methyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(C)CCC2 JQLVCHDTPJYDIN-UHFFFAOYSA-N 0.000 description 1
- JMAKRFSLJOYECP-UHFFFAOYSA-N 1-propyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound C(CC)C1CCCC=2C(C3=CC=CC=C3C(C12)=O)=O JMAKRFSLJOYECP-UHFFFAOYSA-N 0.000 description 1
- QDQRAKVTIKNTPJ-UHFFFAOYSA-N 1-propylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCC QDQRAKVTIKNTPJ-UHFFFAOYSA-N 0.000 description 1
- LUYMZLHJNJOZQV-UHFFFAOYSA-N 2,3-dimethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(C)C(C)C2 LUYMZLHJNJOZQV-UHFFFAOYSA-N 0.000 description 1
- KIJPZYXCIHZVGP-UHFFFAOYSA-N 2,3-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C(C)=C2 KIJPZYXCIHZVGP-UHFFFAOYSA-N 0.000 description 1
- ZRYMONUIRTWHAP-UHFFFAOYSA-N 2,7-dimethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC(C)=CC=C2C(=O)C2=C1CC(C)CC2 ZRYMONUIRTWHAP-UHFFFAOYSA-N 0.000 description 1
- RATJDSXPVPAWJJ-UHFFFAOYSA-N 2,7-dimethylanthracene-9,10-dione Chemical compound C1=C(C)C=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 RATJDSXPVPAWJJ-UHFFFAOYSA-N 0.000 description 1
- WUEMGYBVEZJPLF-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(C(C)(C)CC)CC2 WUEMGYBVEZJPLF-UHFFFAOYSA-N 0.000 description 1
- WUKWGUZTPMOXOW-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)CC)=CC=C3C(=O)C2=C1 WUKWGUZTPMOXOW-UHFFFAOYSA-N 0.000 description 1
- XFMXZXLBJNGKGK-UHFFFAOYSA-N 2-butan-2-yl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(C(C)CC)CC2 XFMXZXLBJNGKGK-UHFFFAOYSA-N 0.000 description 1
- MCYPCBFOVKMNDW-UHFFFAOYSA-N 2-butan-2-ylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)CC)=CC=C3C(=O)C2=C1 MCYPCBFOVKMNDW-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- WJCQJHNUBJYFBW-UHFFFAOYSA-N 2-methyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(C)CC2 WJCQJHNUBJYFBW-UHFFFAOYSA-N 0.000 description 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- JBIIAJUNHWBZRG-UHFFFAOYSA-N 2-propan-2-yl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(C(C)C)CC2 JBIIAJUNHWBZRG-UHFFFAOYSA-N 0.000 description 1
- BQUNPXRABCSKJZ-UHFFFAOYSA-N 2-propan-2-ylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3C(=O)C2=C1 BQUNPXRABCSKJZ-UHFFFAOYSA-N 0.000 description 1
- GRVQOVOAEKOZNN-UHFFFAOYSA-N 2-propyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound C(CC)C1CC=2C(C3=CC=CC=C3C(C2CC1)=O)=O GRVQOVOAEKOZNN-UHFFFAOYSA-N 0.000 description 1
- ZPQUFYIADDJOEF-UHFFFAOYSA-N 2-propylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCC)=CC=C3C(=O)C2=C1 ZPQUFYIADDJOEF-UHFFFAOYSA-N 0.000 description 1
- RONQEQAXCQKPRV-UHFFFAOYSA-N 2-tert-butyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(C(C)(C)C)CC2 RONQEQAXCQKPRV-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- AGWLDLJEVPKXBR-UHFFFAOYSA-N 4,4-dimethyl-2,3-dihydro-1H-anthracene-9,10-dione Chemical compound CC1(CCCC=2C(C3=CC=CC=C3C(C12)=O)=O)C AGWLDLJEVPKXBR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AYEQTYDDOFANHS-UHFFFAOYSA-N O=C1C2=CC=CC=C2C(=O)C2=C1CC(C(C)CCC)CC2 Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(C(C)CCC)CC2 AYEQTYDDOFANHS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XAIKOVRFTSBNNU-UHFFFAOYSA-N anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 XAIKOVRFTSBNNU-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000002592 cumenyl group Chemical class C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical class O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- 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
- C01B15/013—Separation; Purification; Concentration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/10—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention provides a kind of method for obtaining high-quality reproduction operation solution from the working solution of three monooctyl ester of phosphoric acid (TOP) removing inert matter.A kind of peroxidating method for preparing hydrogen includes: hydrogen peroxide manufacturing process, it is aoxidized after being hydrogenated containing the working solution of aromatic hydrocarbon, TOP and Anthraquinones, hydrogen peroxide is thus generated, it is extracted from working solution, the working solution after extracting hydrogen peroxide returns to hydrogenation process circulation；The inert matter of generation by-product with hydrogen peroxide is removed from working solution, prepares thick reproduction operation solution by step for regeneration of working solution；Alkali cleaning is carried out to thick reproduction operation solution, the process for preparing circulation reproduction operation solution, step for regeneration of working solution includes: i) by the first distillation process of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or its pressure below；Ii) then by a lower pressure and 160 DEG C or more carry out distillation recovery Anthraquinones and TOP after-fractionating processes.
Description
Technical field
The present invention relates to the peroxidating method for preparing hydrogen for using Anthraquinones, especially include the step for regeneration of working solution
Peroxidating method for preparing hydrogen.
Background technique
Hydrogen peroxide is with oxidability and has strong bleaching and bactericidal effect, therefore is used as paper, paper pulp, fiber
Deng bleaching agent, fungicide etc..Since the decomposition product of hydrogen peroxide is water and oxygen, thus from the viewpoint of Green Chemistry
Be also imparted with consequence, especially as chlorine system bleaching agent alternative materials and attract attention.In addition, in semiconductor substrate
Deng surface clean, in the semiconductor industries such as the etching of chemical grinding, electronic loop of copper, tin and other copper alloy surface,
The usage amount of hydrogen peroxide also incrementally increases.Also, it is widely used in turning to the oxidation reaction of representative with epoxidation and hydroxyl
In, hydrogen peroxide is important industrial product.
As industrial peroxidating method for preparing hydrogen, it is known that anthraquinone.In the method, Anthraquinones have been dissolved in
Working solution is obtained in solvent, and anthraquinone type hydrogenation is generated into anthracene two in the presence of a hydrogenation catalyst in hydrogenation process
Phenols.Then, oxanthranol class is again converted to Anthraquinones in oxidation operation, while generates hydrogen peroxide.In working solution
Hydrogen peroxide benefit the methods of be extracted with water and to be separated from working solution.Working solution after extracting hydrogen peroxide again returns to
Hydrogenation process forms circulation technology.
Be repeated by anthraquinone type hydrogenation contained in working solution be oxanthranol class, again be oxidized as Anthraquinones and
During the operation for manufacturing hydrogen peroxide, generation does not have contributive tetrahydro-anthraquinone epoxides, four to the generation of hydrogen peroxide
Monomer by-product, the solvent adduct of Anthraquinones and the polymer of Anthraquinones of the Anthraquinones such as hydroxyl anthrone, hydroxyl anthrone, anthrone
Deng.Also generate the degraded matter of solvent composition.Such ingredient unrelated with the manufacture of hydrogen peroxide is classified as " nonactive object
Matter ".The increase of the inert matter becomes the reason of concentration decline of active material Anthraquinones etc., makes each process of circulation technology
Ability decline.Therefore, the concentration of demand inert matter is low, the concentration of active material can be maintained sufficiently high state
Working solution (patent document 1).
Existing technical literature
Patent document
Patent document 1:WO2007/129769
Summary of the invention
Technical problems to be solved by the inivention
The group origin cause of formation hydrogen peroxide manufacturing equipment of working solution and it is different, but use mostly and contains aromatic hydrocarbon as nonpolar
Solvent, containing tri-2-ethylhexyl phosphate (CAS number: 78-42-2, hereinafter sometimes referred to as " trioctyl phosphate " or
" TOP ") as polar solvent, contain the working solution of alkyl-anthraquinone and alkyl tetrahydro anthraquinone as Anthraquinones.But containing
Trioctyl phosphate inhibits the concentration of inert matter as being had not been reported in the working solution of polar solvent so far, will live
The method that the concentration of property substance maintains sufficiently high state.Therefore, one of the objects of the present invention is to provide one kind from utilization
Inert matter is removed in working solution use when anthraquinone manufacture hydrogen peroxide, containing trioctyl phosphate, maintains or changes
It is apt to the physical property and/or active method of the working solution.
For solving the technical solution of technical problem
In order to solve the above problems, the present inventor has made intensive studies, as a result, it has been found that from aromatic series is contained
The method of by-product is removed in the working solution of hydrocarbon, trioctyl phosphate and Anthraquinones.In the method, by atmospheric pressure or greatly
The distillation recovery aromatic hydrocarbon carried out under air pressure pressure below then passes through at much lower pressure and 160 DEG C or more carries out
Distillation recovery Anthraquinones and trioctyl phosphate, using whole distillates of recycling as working solution recycle.Also, the present invention
Inventor continue to study, discovery pass through to after regeneration working solution carry out alkali cleaning, hydrogenation activity improve.
One aspect of the present invention is as follows.
[1] a kind of peroxidating method for preparing hydrogen characterized by comprising
Hydrogen peroxide manufacturing process, it is laggard by being hydrogenated containing the working solution of aromatic hydrocarbon, trioctyl phosphate and Anthraquinones
Row oxidation, thus generates hydrogen peroxide, the hydrogen peroxide is extracted from working solution, the working solution after extracting the hydrogen peroxide
It returns in hydrogenation process, is recycled；
Step for regeneration of working solution, by the inert matter generated with the generation of above-mentioned hydrogen peroxide as by-product from
It is removed in above-mentioned working solution, prepares the thick reproduction operation solution after the inert matter is removed；With
Circulation reproduction operation solution preparation section carries out alkali cleaning to above-mentioned thick reproduction operation solution, and preparation circulation is used
Reproduction operation solution,
Above-mentioned step for regeneration of working solution includes:
I) by the first distillation work of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or atmospheric pressure pressure below
Sequence；With
Ii) then by much lower pressure and 160 DEG C or more the distillation recovery Anthraquinones and trioctyl phosphate carried out
After-fractionating process.
[2] the peroxidating method for preparing hydrogen as described in [1], wherein the pressure in above-mentioned first distillation process is in 1kPa
In the range of~100kPa.
[3] the peroxidating method for preparing hydrogen as described in [1] or [2], wherein the pressure in above-mentioned after-fractionating process exists
1kPa or less.
[4] the peroxidating method for preparing hydrogen as described in any one of [1]~[3], wherein in above-mentioned after-fractionating process
Temperature in the range of 160 DEG C~300 DEG C.
[5] the peroxidating method for preparing hydrogen as described in any one of [1]~[4], wherein above-mentioned Anthraquinones include alkyl
Anthraquinone and alkyl tetrahydro anthraquinone.
[6] the peroxidating method for preparing hydrogen as described in any one of [1]~[5], wherein including using again above-mentioned circulation
Raw working solution returns to the process in hydrogen peroxide manufacturing process.
[7] the peroxidating method for preparing hydrogen as described in [6], wherein the solvent ratio of components of above-mentioned thick reproduction operation solution
Solvent ratio of components relative to the working solution recycled in hydrogen peroxide manufacturing process is in the range of ± 20 percentage point.
[8] the peroxidating method for preparing hydrogen as described in [6] or [7], wherein the anthraquinone in above-mentioned thick reproduction operation solution
The concentration of class is the full of the concentration of the Anthraquinones in the working solution recycled in hydrogen peroxide manufacturing process or more and Anthraquinones
In the range below concentration.
[9] the peroxidating method for preparing hydrogen as described in any one of [6]~[8], wherein in above-mentioned circulation regeneration work
Make in solution preparation section, reproduction operation solution is adjusted to the 20%~160% of saturated water component.
[10] the peroxidating method for preparing hydrogen as described in any one of [6]~[9], wherein above-mentioned circulation regeneration work
Making solution preparation section further includes the process washed to the reproduction operation solution after alkali cleaning.
[11] the peroxidating method for preparing hydrogen as described in any one of [1]~[10], wherein further include from above-mentioned second
The process of separating anthraquinone and trioctyl phosphate in the distillate of distillation process.
[12] the peroxidating method for preparing hydrogen as described in [11], wherein above-mentioned separating anthraquinone and trioctyl phosphate
Process is carried out using recrystallization.
[13] a kind of hydrogen peroxide manufacture system, for destilling tower, preparation vessel, rinse bath, hydrogenation tower, oxidizing tower and
The hydrogen peroxide manufacture system of extraction column, wherein
Destilling tower have unknown ingredient discharge pipe, destilling tower and preparation vessel by leading portion distill distillate supply pipeline with
Back segment distills the connection of distillate supply pipeline, and preparation vessel is connected to rinse bath by thick reproduction operation solution feed line, cleans
Slot is connected with aqueous slkali supply pipeline and water supplying pipe line, and rinse bath has waste liquid pipeline, and rinse bath and hydrogenation tower pass through circulation
It is connected to reproduction operation solution feed line, hydrogenation tower is connected with hydrogenant agent supply pipeline, hydrogenates tower and oxidizing tower passes through hydrogenation
The connection of working solution supply pipeline, it is molten by oxidation work that oxidizing tower is connected with oxidant supply pipeline, oxidizing tower and extraction column
Liquid supply pipeline connection, after there is extraction column hydrogen peroxide feed-line, destilling tower and extraction column to be extracted by hydrogen peroxide
The supply pipeline of working solution is connected to.
[14] system as described in [13], wherein also there is leading portion to distill distillate tank, destilling tower and leading portion distillate
Object tank distills the connection of distillate feed-line by leading portion, and leading portion distills distillate tank and preparation vessel and distills distillate by leading portion
Supply pipeline connection.
[15] system as described in [13], wherein also there is back segment to distill distillate tank, destilling tower and back segment distillate
Object tank distills the connection of distillate feed-line by back segment, and back segment distills distillate tank and preparation vessel and distills distillate by back segment
Supply pipeline connection.
[16] system as described in [13], wherein also there is recrystallization slot, recrystallization slot has filter and sewer pipe
Line, recrystallization slot are connected with recrystallization solvent supply pipeline, recrystallize slot and destilling tower by back segment and distill distillate supply pipe
Line connection, recrystallization slot are connected to preparation vessel by Anthraquinones supply pipeline.
Invention effect
The present invention can be realized a kind below or more of effect.
(1) it can be removed from working solution that have accumulated inert matter, to contain trioctyl phosphate as polar solvent
Remove the inert matter.
(2) it can efficiently recycle from containing in working solution of the trioctyl phosphate as polar solvent as active material
Anthraquinones, recycled.
(3) by reducing the inert matter in cycle operation solution, the effect for each process that hydrogen peroxide can be manufactured
Rate is maintained at higher state.
(4) viscosity that can will cycle for solution maintains reduced levels.
(5) hydrogenation activity that can will cycle for solution maintains higher state.
(6) it can be applied to the working solution of high three monooctyl ester of phosphoric acid of frequency of use, thus have a wide range of application, it being capable of the phase
To make great contribution to the efficient activity that hydrogen peroxide manufactures.
Detailed description of the invention
Fig. 1 is the schematic diagram of a mode of hydrogen peroxide manufacture system of the invention.
Fig. 2 is the schematic diagram of a mode of the hydrogen peroxide manufacture system of the invention with recrystallization slot.
Symbol description
1: destilling tower；2: preparation vessel；3: rinse bath；4: hydrogenation tower；5: oxidizing tower；6: extraction column；7: distillate delivery pipe
Line；7a: leading portion distills distillate feed-line；7b: back segment distills distillate feed-line；7c: TOP feed-line is distillated；7d:
Distillate recrystallization solvent feed-line；8: unknown ingredient discharge pipe；9: leading portion distills distillate tank；10: back segment distillates
Object tank；11: leading portion distills distillate supply pipeline；12: back segment distills distillate supply pipeline；13: thick reproduction operation solution supplies
To pipeline；14: aqueous slkali supply pipeline；15: water supplying pipe line；16: circulation reproduction operation solution feed line；17: waste liquid
Pipeline；18: hydrogenant agent pipeloop；19: hydrogenant agent supply pipeline；20: hydrogenated work solution supply pipeline；21: oxidant supplies
To pipeline；22: exhaust line；23: oxidation working solution supply pipeline；24: water supplying pipe line；25: hydrogen peroxide feed-line；
26: the supply pipeline of the working solution after hydrogen peroxide extraction；27: the pipeloop of the working solution after hydrogen peroxide extraction；
28: unknown ingredient；29: aqueous slkali；30: water；31: waste liquid；32: hydrogenant agent；33: oxidant；34: unreacted oxidant；35:
Water；36: aquae hydrogenii dioxidi；37: recrystallization slot；38: recrystallization solvent tank；39: recrystallization solvent supply pipeline；40: Anthraquinones
Supply pipeline；41: waste liquid pipeline；42: filtrate feed-line；V: valve.
Specific embodiment
One embodiment of the present invention is related to a kind of peroxidating method for preparing hydrogen (hereinafter sometimes referred to " peroxide of the invention
Change hydrogen manufacturing method ") characterized by comprising
Hydrogen peroxide manufacturing process (will go back containing the hydrogenation of the working solution of aromatic hydrocarbon, trioctyl phosphate and Anthraquinones
It is former) after aoxidized, thus generate hydrogen peroxide, the hydrogen peroxide extracted from working solution, after extracting the hydrogen peroxide
Working solution returns in hydrogenation process, is recycled；
Step for regeneration of working solution, by the inert matter generated with the generation of above-mentioned hydrogen peroxide as by-product from
It is removed in above-mentioned working solution, prepares the thick reproduction operation solution after the inert matter is removed；With
Circulation reproduction operation solution preparation section carries out alkali cleaning to above-mentioned thick reproduction operation solution, and preparation circulation is used
Reproduction operation solution,
Above-mentioned step for regeneration of working solution includes:
I) by the first distillation work of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or atmospheric pressure pressure below
Sequence；With
Ii) then by much lower pressure and 160 DEG C or more the distillation recovery Anthraquinones and trioctyl phosphate carried out
After-fractionating process.
It as aromatic hydrocarbon contained by working solution, does not limit, such as the virtue at least replacing and having 1 alkyl can be enumerated
Fragrant race's hydrocarbon, particularly alkylbenzene (such as trimethylbenzene containing 9 carbon atoms etc.) containing 8,9,10,11 or 12 carbon atoms
Or mixtures thereof etc., it is preferably able to the compound for dissolving anthraquinone.In specific mode, aromatic hydrocarbon is selected from carbon atom number
The mixed solvent (such as cumene isomer mixture) that 10 mixed solvent and carbon atom number is 9.As polar solvent
Trioctyl phosphate is the compound having following structure.
Anthraquinones contained by working solution contain can be by anthraquinone anthraquinone (the 9,10- anthracene two for generating hydrogen peroxide
Ketone), it is at least one kind of in tetrahydro-anthraquinone and its derivative.As the derivative for the anthraquinone that can generate hydrogen peroxide, do not limit
It is fixed, such as alkyl-anthraquinone can be enumerated.Alkyl-anthraquinone means at least to replace the anthraquinone for having 1 alkyl.In specific mode, alkane
Base anthraquinone include 1,2 or 3 at least one at replaced by the aliphatic substitution of the linear chain or branched chain at least containing 1 carbon atom
Anthraquinone.Alkyl substituent in alkyl-anthraquinone preferably comprises 1~9, more preferable 1~6 carbon atom.As alkyl-anthraquinone
Concrete example does not limit, such as can enumerate tectoquinone (2-methylanthraquinone etc.), dimethyl anthraquinone (1,3- dimethylanthracene
Quinone, 2,3- dimethyl anthraquinone, 1,4- dimethyl anthraquinone, 2,7- dimethyl anthraquinone etc.), ethyl hydrazine (2- ethyl hydrazine
Deng), propyl anthraquinone (2- n-propyl anthraquinone, 2- isopropyl anthraquinone etc.), butyl anthraquinone (2- sec-butyl anthraquinone, 2- tert-butyl
Anthraquinone etc.), amyl anthraquinone (2- amylanthraquinone, 2- tertiary pentyl anthraquinone etc.) etc..As preferred alkyl-anthraquinone, can enumerate
Ethyl hydrazine, amyl anthraquinone or their mixture.The concentration of alkyl-anthraquinone class in working solution can be according to the shape of technique
Condition is controlled, such as is used in the concentration range of 0.4~1.0mol/L etc..
It as the derivative for the tetrahydro-anthraquinone that can generate hydrogen peroxide, does not limit, such as alkyl tetrahydro can be enumerated
Anthraquinone.Alkyl tetrahydro anthraquinone means at least to replace the tetrahydro-anthraquinone for having 1 alkyl.In specific mode, alkyl tetrahydro anthraquinone
Including the tetrahydro replaced at least the one of 1,2 or 3 by the aliphatic substitution of the linear chain or branched chain at least containing 1 carbon atom
Anthraquinone.Alkyl substituent in alkyl tetrahydro anthraquinone preferably comprises 1~9, more preferable 1~6 carbon atom.As alkyl tetrahydro
The concrete example of anthraquinone, does not limit, such as can enumerate methyl tetrahydro-anthraquinone (2- methyl tetrahydro-anthraquinone etc.), dimethyl tetrahydro
Anthraquinone (1,3- dimethyl tetrahydro anthraquinone, 2,3- dimethyl tetrahydro anthraquinone, 1,4- dimethyl tetrahydro anthraquinone, 2,7- dimethyl
Tetrahydro-anthraquinone etc.), ethyl tetrahydro-anthraquinone (2- ethyl tetrahydro-anthraquinone etc.), propyl tetrahydro-anthraquinone (2- n-propyl tetrahydro-anthraquinone,
2- isopropyl tetrahydro-anthraquinone etc.), butyl tetrahydro-anthraquinone (2- sec-butyl tetrahydro-anthraquinone, 2- tert-butyl tetrahydro-anthraquinone etc.), amyl
Tetrahydro-anthraquinone (2- sec-amyl tetrahydro-anthraquinone, 2- tertiary pentyl tetrahydro-anthraquinone etc.) etc..It, can be with as preferred alkyl tetrahydro anthraquinone
Enumerate ethyl tetrahydro-anthraquinone, amyl tetrahydro-anthraquinone or their mixture.
In a mode, working solution contains the combination of alkyl-anthraquinone and alkyl tetrahydro anthraquinone.Alkyl in the combination
The molar ratio of anthraquinone and alkyl tetrahydro anthraquinone is not particularly limited, and is indicated with alkyl En Kun ﹕ alkyl tetrahydro anthraquinone, preferably
0.05 ﹕, 1~100 ﹕ 1, more preferably 0.1 ﹕, 1~75 ﹕ 1, further preferably 0.2 ﹕, 1~50 ﹕ 1.Also, alkyl-anthraquinone and alkyl
The weight ratio of tetrahydro-anthraquinone is also not particularly limited, and is indicated with alkyl En Kun ﹕ alkyl tetrahydro anthraquinone, 1~100 ﹕ of preferably 0.05 ﹕
1,0.1 ﹕, 1~75 ﹕ 1, further preferably 0.2 ﹕, 1~50 ﹕ 1 are more preferably.Particularly preferred alkyl-anthraquinone and alkyl tetrahydro anthracene
The combination of quinone is the combination of ethyl hydrazine and ethyl tetrahydro-anthraquinone.
Hydrogen peroxide manufacturing process can carry out according to the known method using anthraquinone manufacture hydrogen peroxide.Peroxidating
Hydrogen manufacturing process typically comprise by working solution hydrogenation process, by after hydrogenation working solution oxidation process and will lead to
The hydrogen peroxide that peroxidating generates extracts the process in water phase.The hydrogenation of working solution for example can be by hydrogenation catalyst
In the presence of, using hydrogeneous gases such as the mixtures of hydrogen or inactive gas (nitrogen etc.) and hydrogen working solution is carried out
Be bubbled etc. come carry out.The oxidation of working solution after hydrogenation for example can be by utilizing the oxygen-containing gas such as air or oxygen to work
Solution be bubbled etc. to carry out.Extraction of the hydrogen peroxide into water phase for example can be by the working solution and water after aoxidizing
Mixing again carries out aqueous phase separation etc..It the processing such as can be refined, be concentrated after the hydrogen peroxide of extraction.
Inert matter is removed in slave working solution in step for regeneration of working solution to carry out by distillation process, distills work
Sequence includes:
I) by the first distillation work of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or atmospheric pressure pressure below
Sequence (is also sometimes referred to as leading portion distillation process) below；With
Ii) then by much lower pressure and 160 DEG C or more the distillation recovery Anthraquinones and trioctyl phosphate carried out
After-fractionating process (below also be sometimes referred to as back segment distillation process).
In the first distillation process, working solution is distilled under atmospheric pressure pressure below, by working solution institute
The aromatic hydrocarbon contained is recycled as distillate.As long as distillation pressure can recycle aromatic hydrocarbon, it is not particularly limited, such as can
Think 0.5kPa~100kPa, 0.8kPa~100kPa, 1kPa~100kPa, 1kPa~50kPa etc..It is preferably able to distill out virtue
Fragrant race's hydrocarbon but the distillation pressure for not distilling out trioctyl phosphate and Anthraquinones.As long as vapo(u)rizing temperature can recycle aromatic hydrocarbon,
Also be not particularly limited, for example, can for 110 DEG C~240 DEG C, 120 DEG C~220 DEG C, 130 DEG C~200 DEG C, 140 DEG C~190 DEG C,
150 DEG C~185 DEG C etc..It is preferably able to the vapo(u)rizing temperature for distilling out aromatic hydrocarbon but not distilling out trioctyl phosphate and Anthraquinones.
The viewpoints such as the rate of recovery from aromatic hydrocarbon consider, in the first distillation process distillation preferably last for no longer distilling out distillate be
Only.The aromatic hydrocarbon distilled out in the first distillation process is reused as the ingredient of reproduction operation solution.
The work that the working solution supplied to the first distillation process typically recycles in hydrogen peroxide manufacturing process is molten
Liquid, the inert matter generated containing the generation with hydrogen peroxide as by-product.The working solution can be in peroxide
The working solution of any stage acquisition of Hua Qing manufacturing process, but considers from a security point, preferably without hydrogen peroxide or
Even if person contains also few (such as working solution of the content after the abstraction process of 0.35g/L or less) of its content.As non-live
Property substance, such as by-product (oxide, decomposition from Anthraquinones or solvent (aromatic hydrocarbon and trioctyl phosphate) can be enumerated
Object etc.).As the by-product from Anthraquinones, such as tetrahydro-anthraquinone epoxides, tetrahydroxy anthrone, hydroxyl anthracene can be enumerated
The monomer by-product of the Anthraquinones such as ketone, anthrone, the solvent adduct of Anthraquinones, polymer of Anthraquinones etc..As from solvent
By-product, such as carboxylic acids, polyalcohols, phenols can be enumerated etc..
In after-fractionating process, for residue obtained in the first distillation process, more lower than the first distillation process
Under pressure and 160 DEG C or more are distilled, and are recycled using Anthraquinones and trioctyl phosphate as distillate.Thereby, it is possible to by boiling point
The by-product (high boiling ingredient) higher than Anthraquinones and trioctyl phosphate removes.As long as distillation pressure can recycle Anthraquinones and phosphoric acid
The pressure of three monooctyl esters, is not particularly limited, for example, can for 0.001kPa~1kPa, 0.002kPa~0.5kPa,
0.005kPa~0.2kPa, 0.008kPa~0.1kPa, 0.1kPa~0.3kPa etc..It is preferred that distilling out Anthraquinones and tricresyl phosphate is pungent
Ester but by-product distillate few distillation pressure.As long as vapo(u)rizing temperature can recycle the temperature of Anthraquinones and trioctyl phosphate i.e.
Can, it is also not particularly limited, such as can be 160 DEG C~300 DEG C, 165 DEG C~280 DEG C, 170 DEG C~270 DEG C, 175 DEG C~260
DEG C, 220 DEG C~260 DEG C etc..In part way, the upper limit of the vapo(u)rizing temperature of after-fractionating process can be lower than 200 DEG C.Cause
This, the range of the vapo(u)rizing temperature of the after-fractionating process in the method for example can for 160 DEG C~199 DEG C, 160 DEG C~198 DEG C,
160 DEG C~197 DEG C, 160 DEG C~196 DEG C, 160 DEG C~195 DEG C, 160 DEG C~194 DEG C, 160 DEG C~193 DEG C, 160 DEG C~192
DEG C, 160 DEG C~191 DEG C, 160 DEG C~190 DEG C, 160 DEG C~189 DEG C, 160 DEG C~188 DEG C, 160 DEG C~187 DEG C, 160 DEG C~
186 DEG C, 160 DEG C~185 DEG C, 160 DEG C~184 DEG C, 160 DEG C~183 DEG C, 160 DEG C~182 DEG C, 160 DEG C~181 DEG C, 160 DEG C
~180 DEG C etc..It is preferred that distill out Anthraquinones and trioctyl phosphate but by-product distillates few vapo(u)rizing temperature.
The viewpoints such as the rate of recovery from Anthraquinones consider that the distillation in after-fractionating process, which preferably lasts for no longer distilling out, to be evaporated
Out until object.In addition, the mean residence time in after-fractionating process is not particularly limited, such as can be at 1 hour or more.
" residence time " means to distillate in distillation process or the kettle residual time from start to stop, and " mean residence time " means carry out 2
The simple arithmetic average of residence time when the secondary above identical distillation process.Mean residence time example in after-fractionating process
It such as can be 1 hour~10 hours ranges, 6 hours~10 hours ranges.By make mean residence time 1 hour with
On, have the advantages that the rate of recovery of Anthraquinones increases, and the by-product from Anthraquinones occurs to hydrogen peroxide life
At the conversion of the Anthraquinones of ability, the amount of the Anthraquinones with hydrogen peroxide generative capacity increases.For example, four as by-product
Hydrogen anthraquinone epoxides can be converted into the tetrahydro-anthraquinone with hydrogen peroxide generative capacity.
The Anthraquinones and trioctyl phosphate distilled out in after-fractionating process are recycled as the ingredient of reproduction operation solution.
As device used in distillation process, as long as the distillation under temperature and pressure as defined in being able to carry out, does not have
Be particularly limited to, such as batch-type distilling apparatus, continous way distilling apparatus, thin-film distillation device can be enumerated etc..From cost etc.
Both distilling apparatus that viewpoint consideration, preferably the first distillation process and after-fractionating process are able to use.
In a mode, process for hydrogen peroxide production of the invention further includes the distillate from above-mentioned after-fractionating process
The process of middle separating anthraquinone and trioctyl phosphate.The separation of Anthraquinones and trioctyl phosphate can be by recrystallizing Anthraquinones
Come carry out.The recrystallization of Anthraquinones can by make Anthraquinones dissolve by heating cooled down after recrystallization solvent come into
Row.After recrystallization, the Anthraquinones of recrystallization can be recycled and be recycled.The trioctyl phosphate separated from Anthraquinones can lead to
Distillation etc. is crossed to separate and recycle from recrystallization solvent.As recrystallization solvent, preferably the solubility of Anthraquinones when heated with
The big solvent of the difference of solubility when cooling.As the non-limiting example of recrystallization solvent, alcohol series solvent (such as first can be enumerated
The lower alcohols such as alcohol, ethyl alcohol, propyl alcohol, isopropanol, butanol, the tert-butyl alcohol, 2-Ethylhexyl Alcohol etc.), use as the ingredient of working solution
Nonpolar solvent (aromatic hydrocarbon etc.) or polar solvent (TOP, diisobutyl carbinol (DIBC), tetrabutyl urea, methylcyclohexyl acetate
Deng) etc..Recrystallization solvent can be made of the solvent of single one kind, be also possible to the mixture of multi-solvents.Recrystallization solvent
The amount that the recrystallization of the preferred Anthraquinones of amount relative to working solution can carry out well, for example, with every list of working solution
Volume (such as g/mL) meter of the solvent of position weight can be 1~20 times, 2~15 times, 3~10 times, 4~8 times etc..Pass through packet
It includes the process of Anthraquinones and trioctyl phosphate separation, Anthraquinones can be recycled in the form of higher purity.Therefore, Neng Goujin
One step reduces the concentration of by-product contained by reproduction operation solution.
The preparation of thick reproduction operation solution in step for regeneration of working solution can be by will recycle in the first distillation process
Aromatic hydrocarbon and after-fractionating process in the Anthraquinones that recycle and trioctyl phosphate mix to carry out.It is including from second
In the mode for the process for separating Anthraquinones and trioctyl phosphate in the distillate of distillation process, the preparation of thick reproduction operation solution
Can by by the aromatic hydrocarbon recycled in the first distillation process and the Anthraquinones being separately recovered after after-fractionating process and
Trioctyl phosphate mixes to carry out.In the present specification, thick reproduction operation solution means containing the fragrance recycled in distillation process
Reproduction operation solution before race's hydrocarbon, trioctyl phosphate and Anthraquinones, progress alkali cleaning.
When solvent ratio of components in working solution changes, density, viscosity, distribution coefficient of working solution etc. also become
Change.When these parameters change, the operating condition and equipment of each process are also required to change, and stablize life from hydrogen peroxide
From the viewpoint of production not preferably.Therefore, the solvent ratio of components of reproduction operation solution is preferably adjusted to and the work in circulation technology
The close value of solution.For example, the solvent ratio of components (%) of reproduction operation solution is preferably adjusted to the work relative to circulation technology
Within ± 20 percentage points of solution, (but the solvent after adjusting within preferably ± 10 percentage points, more preferably within ± 5 percentage points
100%) the total of ratio of components is no more than.That is, the solvent of working solution is made of aromatic hydrocarbon and trioctyl phosphate, in circulation industrial
In the case where solvent ratio of components (volume ratio) Fang Xiang race hydrocarbon ﹕ trioctyl phosphate=70% ﹕ 30% in skill, it is desirable to by reproduction operation
The solvent ratio of components of solution be adjusted to 90% ﹕, 10%~50% ﹕ 50%, preferably 80% ﹕, 20%~60% ﹕ 40%, more preferably
75% ﹕, 25%~65% ﹕ 35%.
In actual equipment, since the concentration of the Anthraquinones of the working solution in circulation technology is reduced year in year out, fit on one side
Locality supplements new Anthraquinones and is operated on one side.In order not to decline the concentration of the Anthraquinones in circulation technology, it is also preferred that with
Anthraquinone concentration in reproduction operation solution is identical as circulation technology or the concentration of Anthraquinones in circulation technology more than and
It is prepared by the saturated concentration of Anthraquinones mode below.For example, containing aromatic hydrocarbon, trioctyl phosphate, ethyl hydrazine and
In the working solution of ethyl tetrahydro-anthraquinone, preferably in reproduction operation solution ethyl hydrazine and adding up to for ethyl tetrahydro-anthraquinone it is dense
Degree is 0.1~1.4mol/L, preferably 0.3~1.2mol/L, prepared by the mode of more preferably 0.5~1.0mol/L.
When preparing thick reproduction operation solution, other than the ingredient recycled in distillation process, can also mix from it
It is one kind or two or more in the aromatic hydrocarbon of his supply source, trioctyl phosphate and Anthraquinones.In specific mode, other are come from
Aromatic hydrocarbon, trioctyl phosphate and/or the Anthraquinones of supply source include commercially available product or newly synthesized substance.
It is molten to thick reproduction operation obtained in step for regeneration of working solution in circulation in reproduction operation solution preparation section
Liquid carries out alkali cleaning, prepares circulation reproduction operation solution.Circulation with reproduction operation solution mean it is after alkali cleans, be particularly suitable for
The reproduction operation solution used in circulation technology.
Alkali cleaning can be carried out by being cleaned using aqueous alkali etc. to thick reproduction operation solution.It is molten as buck
Alkali contained by liquid, preferably alkalinous metal.Alkalinous metal used in cleaning can be the alkali metal of periodic table of elements group ia,
Preferably lithium, sodium or potassium.Reagent containing them is not particularly limited, may be exemplified lithium hydroxide, sodium hydroxide, sodium carbonate,
Sodium bicarbonate, Boratex, sodium pyrophosphate, kodalk, sodium nitrite, sodium perborate, dibastic sodium phosphate, sodium metasilicate, sodium disilicate,
Three sodium metasilicate, sodium stannate, vulcanized sodium, sodium thiosulfate, sodium tungstate, potassium hydroxide, potassium borohydride, potassium carbonate, potassium cyanide, nitrous
Sour potassium, potassium phenate, potassium hydrogen phosphate, potassium pyrophosphate, potassium stannate etc..Ingredient contained by aqueous alkali is preferably lithium hydroxide, hydrogen-oxygen
Change sodium, sodium carbonate, sodium bicarbonate, potassium hydroxide, more preferably sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, it is special
It You Xuanwei not sodium hydroxide, sodium carbonate, sodium bicarbonate.The pH of aqueous alkali containing alkalinous metal is preferably 8 or more, more preferably
It is 10 or more, particularly preferably 12 or more.
Thick contact of the reproduction operation solution with aqueous alkali for example can by with relative to thick 1 volume of reproduction operation solution
Part contacts for aqueous alkali more than 0.2 times of volume part to carry out.It is preferred that making thick reproduction operation solution and 0.3 times of volume part or more
Aqueous alkali contact.As the method for contact, generally well-known mixed media can be used.Such as have stirring, vibration and
Using the bubbling of inactive gas, parallel flow contact method and counter current contacting method etc., but these are not limited to, as long as can make thick
The method that reproduction operation solution is effectively contacted with aqueous alkali.In addition, the capacity of the aqueous alkali contacted is not tight
The upper limit of lattice can suitably be selected according to the situation of the device and operation that are contacted.
The time of contact of thick reproduction operation solution and aqueous alkali is for example 1 minute or more, more preferable 3 minutes or more, spy
It not preferably 5 minutes or more, can suitably be selected according to the situation of the device and operation that are contacted.Thick reproduction operation solution and alkali
The Contact Temperature of aqueous solution is, for example, 0 DEG C~70 DEG C of range, preferably 10 DEG C~60 DEG C of range, 20 DEG C~50 DEG C particularly preferred
Range.Pressure in the contact treatment of thick reproduction operation solution and aqueous alkali is not particularly limited, and generally is suitable for being maintained at
Normal pressure.Aqueous alkali after terminating contact is separated and is discharged from thick reproduction operation solution.Alkali cleaning can carry out 1 time or more, example
It can such as carry out 1 time, 2 times or 3 times or more.
It can be improved again compared with the case where being cleaned merely with water by carrying out alkali cleaning to reproduction operation solution
The hydrogenation activity of raw working solution.Also, it in the case where thick reproduction operation solution contains acid impurities, is cleaned by alkali, also
Have the advantages that acid impurities can be removed.
In a mode, in circulation in reproduction operation solution preparation section, by the amount of moisture of thick reproduction operation solution
It is adjusted to the 20%~160% of saturated water component.In the hydrogenation process in hydrogen peroxide manufacturing process, working solution it is aqueous
Amount is preferably about 50%~about 95% of the saturated concentration under hydrogenation temperature.It is prepared by the distillate recycled in distillation process thick
The water content of reproduction operation solution is low, and there are the slow-footed tendencies of hydrogenation.It is therefore preferable that returning to the circulation of circulation technology
It is higher than thick reproduction operation solution with the water content of reproduction operation solution.By being carried out using aqueous alkali to thick reproduction operation solution
The water content of reproduction operation solution, can be increased near saturated water component by cleaning.Expection is being unable to reach using alkali cleaning
Moisture range when, can by dehydration, supplement water, using water clean etc. adjusting water content.
In circulation in reproduction operation solution preparation section, other than carrying out alkali cleaning, can also be carried out using water clear
It washes.Water used in cleaning is preferably distilled water, ion exchange water, using the water of the purifications such as anti-impregnating method, it is also preferred that using benefit
The water refined with method other than the above.As water used in cleaning, particularly preferred pure water.Using water carry out cleaning in addition to
It uses water as other than cleansing medium, can clean and be carried out similarly with alkali.Therefore, appearance of the water phase for thick reproduction operation solution
Amount, with the contact gimmick of thick reproduction operation solution, time of contact, Contact Temperature, contact press etc. with for alkali clean on state
It is bright identical.The cleaning carried out using water can be carried out before alkali cleaning, can also be carried out after alkali cleaning, can also be in alkali
It is both carried out before cleaning and after alkali cleaning.It can be carried out 1 time or more using the cleaning that water carries out, such as 1 can be carried out
Secondary, 2 times or 3 times or more.
In circulation in reproduction operation solution preparation section, other than alkali cleaning, can also be utilized by from anthracene
The processing that the regenerated catalyst of the by-product regeneration Anthraquinones of quinones carries out.It can be passed through using the processing that regenerated catalyst carries out
Reproduction operation solution before alkali cleaning or after alkali cleaning, which is passed through addition, has fixed bed or the thermopnore of regenerated catalyst to carry out.
There is a situation where when using 1 logical liquid insufficient, thus preferably carries out recycling logical liquid.It is preferably active as regenerated catalyst
Aluminium oxide or silica alumina, more preferable activated alumina.The surface area and partial size of regenerated catalyst can be according to reactions
Condition and device suitably select, and are not particularly limited.Reaction temperature is preferably 0 DEG C~200 DEG C of range, more preferable 50 DEG C~
150℃.In addition, hydroquinones accumulation, partial regeneration reaction postpone, thus preferably logical in circulation due to the progress of reaction
It contacts during liquid with oxygen or air to aoxidize hydroquinones.And it is possible on one side gradually by the hydrogen peroxide generated at this time
Removing carries out on one side.
In a mode, process for hydrogen peroxide production of the invention includes returning to above-mentioned circulation reproduction operation solution
To the process in hydrogen peroxide manufacturing process.Included by circulation may return to hydrogen peroxide manufacturing process with reproduction operation solution
Hydrogenation process, oxidation operation, arbitrary 1 or more process in abstraction process.Here, meaning to return back to certain process
The arbitrary stage to the stage terminated from the process before the process, until the stage before the process terminates.For example,
Circulation reproduction operation solution is set to mean to return to circulation reproduction operation solution from abstraction process knot back to hydrogenation process
(such as the outlet or hydrogenation of extraction element of arbitrary stage from the stage of beam, until the stage before hydrogenation process terminates
The entrance of device).In specific mode, circulation returns to hydrogenation process with reproduction operation solution.Which can be effectively
Using the high hydrogenation activity of circulation reproduction operation solution, it is advantageous in this regard.It, can as the concrete example of which
To enumerate nearby mixing circulation reproduction operation solution with the working solution in circulation in hydrogenation apparatus (hydrogenation tower), by institute
Obtained mixed liquor imports hydrogenation apparatus.In other specific mode, circulation reproduction operation solution returns to oxidation work
Sequence and/or abstraction process.Which is advantageous in the case where circulation is low with the water content of reproduction operation solution.
Another way of the invention is related to a kind of manufacturing method (hereinafter sometimes referred to " this of circulation reproduction operation solution
The circulation of invention reproduction operation solution manufacturing method ") characterized by comprising
Step for regeneration of working solution, from the life containing aromatic hydrocarbon, trioctyl phosphate, Anthraquinones and adjoint hydrogen peroxide
Hydrogen peroxide manufacture at the inert matter generated as by-product is prepared with above-mentioned inert matter is removed in working solution
The inert matter be removed after thick reproduction operation solution；With
Circulation reproduction operation solution preparation section carries out alkali cleaning to above-mentioned thick reproduction operation solution, and preparation circulation is used
Reproduction operation solution,
Above-mentioned step for regeneration of working solution includes:
I) by the first distillation work of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or atmospheric pressure pressure below
Sequence；With
Ii) then by much lower pressure and 160 DEG C or more the distillation recovery Anthraquinones and trioctyl phosphate carried out
After-fractionating process.
The feature and hydrogen peroxide system of the invention of each process of circulation reproduction operation solution manufacturing method of the invention
The correspondence process made in method is identical.
Another mode of the invention is related to a kind of peroxidating method for preparing hydrogen (hereinafter sometimes referred to " peroxide of the invention
Change hydrogen manufacturing method A ") characterized by comprising
Hydrogen peroxide manufacturing process, it is laggard by being hydrogenated containing the working solution of aromatic hydrocarbon, trioctyl phosphate and Anthraquinones
Row oxidation, thus generates hydrogen peroxide, the hydrogen peroxide is extracted from working solution, the working solution after extracting the hydrogen peroxide
It returns in hydrogenation process, is recycled；
Step for regeneration of working solution, by the inert matter generated with the generation of above-mentioned hydrogen peroxide as by-product from
It is removed in above-mentioned working solution, prepares reproduction operation solution；With
Circulation reproduction operation solution preparation section, cleans above-mentioned thick reproduction operation solution using water or alkali, makes
Standby circulation reproduction operation solution,
Above-mentioned step for regeneration of working solution includes:
I) by the first distillation work of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or atmospheric pressure pressure below
Sequence；With
Ii) then by much lower pressure and 160 DEG C or more the distillation recovery Anthraquinones and trioctyl phosphate carried out
After-fractionating process.
Which is compared with process for hydrogen peroxide production of the invention, it is not necessary to which the alkali for carrying out thick reproduction operation solution is clear
It washes, and can be substituted by the cleaning that water carries out, different next to that is in addition identical.As shown in example 4, even if merely with
Water cleans thick reproduction operation solution, compared with the working solution in circulation, also can be improved containing trioctyl phosphate
The hydrogenation activity of reproduction operation solution.Above-mentioned record involved in process for hydrogen peroxide production of the invention, cleaning in alkali is not
Under the premise of necessary, it is also applied for process for hydrogen peroxide production A of the invention.
Alternative to the present invention is related to a kind of manufacturing method of circulation reproduction operation solution (hereinafter sometimes referred to
" circulation of the invention reproduction operation solution manufacturing method A ") characterized by comprising
Step for regeneration of working solution, from the life containing aromatic hydrocarbon, trioctyl phosphate, Anthraquinones and adjoint hydrogen peroxide
Hydrogen peroxide manufacture at the inert matter generated as by-product is prepared with above-mentioned inert matter is removed in working solution
The inert matter be removed after thick reproduction operation solution；With
Circulation reproduction operation solution preparation section, cleans above-mentioned thick reproduction operation solution using water or alkali, makes
Standby circulation reproduction operation solution,
Above-mentioned step for regeneration of working solution includes:
I) by the first distillation work of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or atmospheric pressure pressure below
Sequence；With
Ii) then by much lower pressure and 160 DEG C or more the distillation recovery Anthraquinones and trioctyl phosphate carried out
After-fractionating process.
The feature and hydrogen peroxide system of the invention of the circulation of the invention each process of reproduction operation solution manufacturing method A
The feature for making corresponding each process in method A is identical.
Other modes of the invention are related to a kind of peroxidating method for preparing hydrogen (hereinafter sometimes referred to " mistake of the invention
Hydrogen oxide manufacturing method B ") characterized by comprising
Hydrogen peroxide manufacturing process carries out after hydrogenating containing the working solution of aromatic hydrocarbon, polar solvent and Anthraquinones
Oxidation, thus generates hydrogen peroxide, the hydrogen peroxide is extracted from working solution, and the working solution after extracting the hydrogen peroxide returns
Into hydrogenation process, recycled；
Step for regeneration of working solution, by the inert matter generated with the generation of above-mentioned hydrogen peroxide as by-product from
It is removed in above-mentioned working solution, prepares reproduction operation solution；With
Circulation reproduction operation solution preparation section carries out alkali cleaning to above-mentioned thick reproduction operation solution, and preparation circulation is used
Reproduction operation solution,
Above-mentioned step for regeneration of working solution includes:
I) by the first distillation work of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or atmospheric pressure pressure below
Sequence；With
Ii) then by much lower pressure and 160 DEG C or more carry out distillation recovery Anthraquinones after-fractionating works
Sequence,
Polar solvent recycles in the first distillation process or after-fractionating process.
Which is compared with process for hydrogen peroxide production of the invention, in addition to polar solvent contained by working solution is not specific
It is identical for recycling other than this two o'clock difference for trioctyl phosphate and polar solvent in the first distillation process or after-fractionating process
's.As shown in example 4, by carrying out alkali cleaning, compared with the case where being cleaned using water, Neng Gouti to thick reproduction operation solution
The hydrogenation activity of high obtained reproduction operation solution, it is believed that this is containing the polar solvent in addition to trioctyl phosphate
It is also such in working solution.The above-mentioned record that process for hydrogen peroxide production of the invention is related to, polar solvent not specifically for
Trioctyl phosphate and under the premise of polar solvent recycles in any process of the first distillation process or after-fractionating process,
It is suitable for the invention process for hydrogen peroxide production B.
As long as the polar solvent in process for hydrogen peroxide production B of the invention can dissolve oxanthranol class, do not have
It is particularly limited to, for example including alcohol (such as diisobutyl carbinol (DIBC) (DIBC), sec-n-octyl alcohol), four substituted ureas (such as tetrabutyl urea
(TBU)), phosphate (such as trioctyl phosphate), 2-Pyrrolidone or acetic acid alkyl ester (such as methylcyclohexyl acetate
(MCHA)) etc..The distillation process of recycling polar solvent can be suitably determined according to the type of polar solvent.Such as DIBC or 2-
Octanol can recycle in the first distillation process, and TOP or TBU can be recycled in after-fractionating process.
Alternative to the present invention is related to a kind of manufacturing method of circulation reproduction operation solution (hereinafter sometimes referred to
" circulation of the invention reproduction operation solution manufacturing method B ") characterized by comprising
Step for regeneration of working solution, from the generation containing aromatic hydrocarbon, polar solvent, Anthraquinones and adjoint hydrogen peroxide
The hydrogen peroxide manufacture of inert matter as by-product generation is somebody's turn to do with above-mentioned inert matter, preparation is removed in working solution
Inert matter be removed after thick reproduction operation solution；With
Circulation reproduction operation solution preparation section carries out alkali cleaning to above-mentioned thick reproduction operation solution, and preparation circulation is used
Reproduction operation solution,
Above-mentioned step for regeneration of working solution includes:
I) by the first distillation work of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or atmospheric pressure pressure below
Sequence；With
Ii) then by much lower pressure and 160 DEG C or more carry out distillation recovery Anthraquinones after-fractionating works
Sequence,
Polar solvent recycles in the first distillation process or after-fractionating process.
The feature and hydrogen peroxide system of the invention of the circulation of the invention each process of reproduction operation solution manufacturing method B
The feature for making corresponding each process in method B is identical.
Another aspect of the present invention relates to one kind to have destilling tower, preparation vessel, rinse bath, hydrogenation tower, oxidizing tower and extraction
The hydrogen peroxide manufacture system (hereinafter sometimes referred to " hydrogen peroxide manufacture system of the invention ") of tower.Hydrogen peroxide of the invention
Manufacture system in addition to that mentioned above, can also have leading portion distillation distillate tank and/or back segment distillation distillate tank.Referring to
Attached drawing is illustrated a mode of hydrogen peroxide manufacture system of the invention.
Fig. 1 shows evaporate with destilling tower 1, preparation vessel 2, rinse bath 3, hydrogenation tower 4, oxidizing tower 5, extraction column 6, leading portion
The hydrogen peroxide manufacture system A of the invention of object tank 9 and back segment distillation distillate tank 10 out.Destilling tower 1 is arranged with unknown ingredient
Pipeline 8 and distillate feed-line 7 out, distillate feed-line 7 and leading portion distillation distillate tank 9 distill distillate by leading portion
Feed-line 7a connection, distillate feed-line 7 and back segment distillation distillate tank 10 distill distillate feed-line by back segment
7b connection, leading portion distill distillate tank 9 and are connected to preparation vessel 2 by leading portion distillation distillate supply pipeline 11, and back segment evaporates
Object tank 10 distills distillate supply pipeline 12 by back segment with preparation vessel 2 and is connected to out, and preparation vessel 2 and rinse bath 3 are by slightly regenerating
Working solution supply pipeline 13 is connected to, and rinse bath 3 is connected with aqueous slkali supply pipeline 14 and water supplying pipe line 15, and rinse bath 3 has
There is waste liquid pipeline 17, rinse bath 3 is connected to hydrogenation tower 4 by circulation reproduction operation solution feed line 16, and hydrogenation tower 4 has
Hydrogenant agent supply pipeline 19 and hydrogenant agent pipeloop 18, hydrogenate tower 4 and oxidizing tower 5 passes through hydrogenated work solution supply pipeline 20
Connection, oxidizing tower 5 have oxidant supply pipeline 21 and exhaust line 22, and oxidizing tower 5 and extraction column 6 pass through oxidation working solution
Supply pipeline 23 is connected to, and extraction column 6 has water supplying pipe line 24 and hydrogen peroxide feed-line 25, and destilling tower 1 and extraction column 6 are logical
The supply pipeline 26 for crossing the working solution after hydrogen peroxide extracts is connected to, circulation reproduction operation solution feed line 16 and peroxide
The supply pipeline 26 for changing the working solution after hydrogen extracts is connected to by the pipeloop 27 of the working solution after hydrogen peroxide extraction.
In addition, leading portion distillation distillate feed-line 7a, back segment distill distillate feed-line 7b, unknown ingredient discharge pipe 8, leading portion
Distill distillate supply pipeline 11, back segment distills distillate supply pipeline 12, thick reproduction operation solution feed line 13, aqueous slkali
Supply pipeline 14, water supplying pipe line 15, circulation reproduction operation solution feed line 16 and waste liquid pipeline 17 have valve V.Distillation
Tower 1 can be realized the vacuum distillation (such as 0.1kPa~15kPa) under various temperature (such as 120 DEG C~260 DEG C).
Working solution in hydrogenation tower 4 with hydrogeneous hydrogenant agent 32 (such as the hydrogen, no from hydrogenant agent supply pipeline 19
Active gas (nitrogen etc.) and mixture of hydrogen etc.) it reacts, oxanthranol class is generated by Anthraquinones.Unreacted hydrogenant agent via
Hydrogenant agent pipeloop 18 is repeatedly fed into hydrogenation tower 4.Working solution after hydrogenation passes through hydrogenated work solution supply pipe
Line 20 enters oxidizing tower 5, oxygen containing oxidant 33 that oxanthranol class is sent from oxidant supply pipeline 21 (such as air, oxygen
Gas etc.) oxidation, generate Anthraquinones and hydrogen peroxide.Unreacted oxidant 34 is discharged from exhaust line 22.It is oxidized and contains
There is the working solution of hydrogen peroxide to enter extraction column 6 by oxidation working solution supply pipeline 23, the hydrogen peroxide of generation because from
Water supplying pipe line 24 supply water 35 and form aquae hydrogenii dioxidi 36, be recovered from hydrogen peroxide feed-line 25.Hydrogen peroxide
A part of working solution after extraction enters destilling tower 1 by the supply pipeline 26 of the working solution after hydrogen peroxide extraction,
It is remaining extracted by hydrogen peroxide after working solution pipeloop 27 and circulation reproduction operation solution feed line 16
Collaborate and returns to hydrogenation tower 4.
It is supplied in into the working solution after the extraction hydrogen peroxide of destilling tower 1 in atmospheric pressure or atmospheric pressure pressure below
The leading portion distillation carried out under power.Distillate, which is distilled, by the leading portion containing aromatic hydrocarbon that leading portion distills out passes through distillate
Feed-line 7 and leading portion distillation distillate feed-line 7a are incorporated in leading portion distillation distillate tank 9.It is remaining in destilling tower 1
Residue, which is supplied in, is distilling the back segment distillation that under low pressure and 160 DEG C or more carry out than leading portion.It is distilled by back segment
Out distillate is distilled by distillate feed-line 7 and back segment containing the back segment of Anthraquinones and trioctyl phosphate distillation distillate
Feed-line 7b is incorporated in back segment distillation distillate tank 10.As back segment distillation test residue unknown ingredient 28 from it is unknown at
Discharge pipe 8 is divided to be discharged.It is accommodated in the leading portion distillation distillate of leading portion distillation distillate tank 9 and is accommodated in back segment distillation distillate
The back segment distillation distillate of tank 10 distills distillate supply pipeline 11 by leading portion respectively and back segment distills distillate supply pipeline
12 enter preparation vessel 2, are mixed, prepare thick reproduction operation solution.Obtained thick reproduction operation solution is by slightly regenerating work
Make solution feed line 13 and enters rinse bath 3.Thick reproduction operation solution utilizes the aqueous slkali supplied from aqueous slkali supply pipeline 14
29 are cleaned, and are cleaned again using the water 30 supplied from water supplying pipe line 15 as needed later, and circulation regeneration is obtained
Working solution.Aqueous slkali used in cleaning or water are discharged as waste liquid 31 from waste liquid pipeline 17.Circulation reproduction operation solution
By circulation reproduction operation solution feed line 16, midway with from hydrogen peroxide extract after working solution circulation pipe
The working solution of line 27 collaborates, into hydrogenation tower 4.
Hydrogen peroxide manufacture system of the invention can also have recrystallization slot.Peroxide of the invention with recrystallization slot
The summary for changing hydrogen production system B is illustrated referring to Fig. 2.Wherein, in hydrogen peroxide manufacture system B, to mistake shown in FIG. 1
It aoxidizes the identical constitutive requirements of hydrogen production system A and marks identical symbol, the description thereof will be omitted.
In this mode, the back segment distillation distillate supply pipeline 12 and recrystallization of back segment distillation distillate tank 10 are connected to
Slot 37 connects, and the Anthraquinones supply pipeline 40 for being connected to recrystallization slot 37 is connect with preparation vessel 2.Slot 37 is recrystallized further to connect
There are recrystallization solvent supply pipeline 39, waste liquid pipeline 41 and filtrate feed-line 42, recrystallization solvent supply pipeline 39 will be tied again
Brilliant solvent tank 38 is connected to recrystallization slot 37, and filtrate feed-line 42 will recrystallize slot 37 and be connected to destilling tower 1.Recrystallization solvent
Tank 38 is connected to by distillating recrystallization solvent feed-line 7d with distillate feed-line 7, and preparation vessel 2 is conveyed by distillating TOP
Pipeline 7c is connected to distillate feed-line 7.Recrystallizing slot 37 has temperature-adjusting device, can be realized Anthraquinones and is recrystallizing
Heating for dissolving in solvent and the recrystallization using the cooling Anthraquinones carried out later.Recrystallizing slot 37 also has filtering
The Anthraquinones of recrystallization can be separated by filtration by device.
In this mode, the back segment distillation distillate for being accommodated in back segment distillation distillate tank 10 distills distillate by back segment
Supply pipeline 12 enters recrystallization slot 37.Recrystallization solvent is supplied from recrystallization solvent supply pipeline 39 to recrystallization slot 37, is led to
It crosses and is cooled down after dissolving by heating Anthraquinones, Anthraquinones contained by back segment distillation distillate recrystallize.Recrystallization
Anthraquinones be recrystallised the filter recycling that slot 37 has, preparation vessel 2 is sent to by Anthraquinones supply pipeline 40.Pass through
Filter, the filtrate containing trioctyl phosphate and recrystallization solvent destilling tower 1 is sent to by filtrate feed-line 42, or
Person is discarded by waste liquid pipeline 41.By distillation, recrystallization solvent and phosphorus are distilled out respectively from the filtrate for being admitted to destilling tower 1
Sour three monooctyl esters, the recrystallization solvent distillated, which passes through distillate feed-line 7 and distillates recrystallization solvent feed-line 7d, to be accommodated in
Recrystallization solvent tank 38, the trioctyl phosphate distillated, which passes through distillate feed-line 7 and distillates TOP feed-line 7c, is sent to system
Standby slot 2.
Hydrogen peroxide manufacture system of the invention is not particularly limited to above explained mode, can want in of the invention
It is made various changes in the range of point.For example, can be the modes such as following in hydrogen peroxide manufacture system A shown in Fig. 1:
(A1) it is not provided with leading portion distillation distillate tank 9 and leading portion connected to it distillation distillate feed-line 7a, is distilled using leading portion
Distillate feed-line 7 is connected to by distillate supply pipeline 11 with preparation vessel 2；(A2) it is not provided with back segment distillation 10 He of distillate tank
Back segment connected to it distills distillate feed-line 7b, distills distillate supply pipeline 12 for distillate delivery pipe using back segment
Line 7 is connected to preparation vessel 2；(A3) leading portion distillation distillate tank 9 and leading portion connected to it distillation distillate delivery pipe are not provided with
Line 7a and back segment distillation distillate tank 10 and back segment connected to it distill distillate feed-line 7b, are distilled using leading portion
Distillate feed-line 7 is connected to by distillate supply pipeline 11 with back segment distillation distillate supply pipeline 12 with preparation vessel 2；(A4)
Be not provided with distillate feed-line 7, leading portion distillation distillate tank 9 and leading portion connected to it distillation distillate feed-line 7a,
And back segment distillation distillate tank 10 and back segment connected to it distill distillate feed-line 7b, distill distillate using leading portion
Destilling tower 1 is connected to by supply pipeline 11 with back segment distillation distillate supply pipeline 12 with preparation vessel 2.
In addition, in hydrogen peroxide manufacture system B shown in Fig. 2, in addition to about the above-mentioned of hydrogen peroxide manufacture system A
Change except (A1)~(A4), such as can also be for such as inferior mode: (B1) is not provided with filtrate feed-line 42 and distillates to tie again
Brilliant solvent line 7d；(B2) setting distillates TOP tank, distillate feed-line 7 and will be evaporated using TOP feed-line 7c is distillated
TOP tank is connected to out, is connected to using distillating TOP supply pipeline and will distillate TOP tank with preparation vessel 2；(B3) it is not set in recrystallization slot 37
Filter is set, and is disposed at the midway of Anthraquinones supply pipeline 40.
Also, it in any system of hydrogen peroxide manufacture system A and B, can according to need at least one pipeline
Pump or additional valve, branch road pipeline are set or remove valve from the pipeline with valve.
Hereinafter, carrying out more specific detail to the present invention using embodiment, but the present invention is not limited to these embodiments.
[embodiment]
< analysis method >
It is pungent to aromatic hydrocarbon, the tricresyl phosphate in sample obtained in working solution and each operation using gas phase chromatographic device
Ester, 2- ethyl hydrazine and 2- ethyl tetrahydro-anthraquinone are quantified.Gas phase chromatographic device uses the gas of Shimadzu Seisakusho Ltd.'s corporation
Phase chromatography GC-2014.Column uses the capillary column DB-5MS of Agilent corporation.It wherein, will be all other than mentioned component
Substance is denoted as " unknown ingredient ".The major part for speculating " unknown ingredient " is inert matter.
The density of initialization solution and circulation reproduction operation solution uses the density ratio of capital of a country Electronics Industry Company
Restatement DA-640 is measured, and viscosity is measured using the Brookfield viscometer that Tokyo gauge company produces.
Initialization solution and circulation are evaluated in accordance with the following methods with the hydrogenation activity of reproduction operation solution.?
Hydrogenation catalyst and working solution are added in 2 mouthfuls of flasks of 100mL.Connect blender in 1 mouth of flask, another 1 mouth with
The connection of hydrogen supply unit.And flask is sealed.Hydrogen supply unit includes hydrogen gauge line, U-shaped tube manometer and water liquid storing part, is being hydrogenated
The height of water liquid storing part is adjusted in reaction according to the variation of the liquid level of U-shaped tube manometer, thus, it is possible to keep flask internal pressure with
Atmospheric pressure is equal.Hydrogen uptake is measured with the difference of the liquid level in hydrogen gauge line.Flask is immersed in 30 DEG C of water-bath, it is quiet
It sets 10 minutes.It is repeated after the exhaust in 3 flasks and hydrogen importing, blender is made to work.Measurement from start absorb hydrogen
Hydrogen uptake after to 30 minutes.Hydrogen uptake is scaled value when 0 DEG C, 1atm.The activity value of hydrogenation catalyst is with per unit
The standard state hydrogen infiltration rate [NmL/ (min × g)] of hydrogenation catalyst weight indicates.Hydrogenation catalyst use 120 DEG C into
2 weight %Pd/ silica 0.05g after row is dry or the 1 weight %Pd/ silica oxidation after being dried at 120 DEG C
Aluminium 0.1g.
Example 1
To implement the first distillation process and after-fractionating process of the invention on a small scale, initialization solution and circulation are used
Reproduction operation solution is compared.
<the first distillation process>
Working solution 400g is added in the 500mL flask that distilling apparatus has.It is distilled under reduced pressure, vacuum degree
Always it controls in 1.3kPa.Temperature in flask is from room temperature to 182 DEG C.Persistently carry out distillation until finally 1.3kPa,
Distillate is no longer distilled out under conditions of 182 DEG C.
<after-fractionating process>
Residue obtained in the first distillation process is distilled under the pressure lower than the first distillation process.Vacuum degree exists
It distills and is changed between a period of time inherence 0.03kPa~0.15kPa started, it is final to stablize in 0.08kPa.Temperature in flask
Degree is from room temperature to 202 DEG C.It persistently carries out distillation and is distillated until finally no longer being distilled out under conditions of 0.08kPa, 202 DEG C
Object.
<distillation result>
The composition of initialization solution and the distillate, residue that are recycled by each distillation process is shown in table 1.As fragrance
Race's hydrocarbon uses higher boiling aromatic naphthas (Swasol 1500, the production of Wan Shan petrochemistry company, CAS No.64742-94-
5) (example 2~4 is also the same).Wherein, in distillation, representative is converted to anthraquinone with tetrahydro-anthraquinone, various reactions occur, because
This, according to ingredient, also weight can increase than initialization solution sometimes.In addition, " waste " indicates the amount being lost in an experiment
(reason may be considered due to the loss etc. in cold-trap or pump).
[table 1]
The composition (material balance) of 1. initialization solution of table and distillate, residue
<evaluation that circulation uses reproduction operation solution>
Reproduction operation solution is prepared by the distillate recycled in each distillation process.It is added in the fraction of after-fractionating process
Thick reproduction operation solution is made to reach the solvent ratio of components close with initialization solution in the fraction of first distillation process.With
The lower composition for indicating initialization solution and thick reproduction operation solution.
[table 2]
The composition of table 2. initialization solution and thick reproduction operation solution
Thick reproduction operation solution is successively utilized to the 30wt% sodium hydrate aqueous solution and 2 times of volumes of 2 times of volumes
Pure water is cleaned, and circulation reproduction operation solution is obtained.Following presentation is molten to initialization solution and circulation reproduction operation
The result that the density of liquid, viscosity, hydrogenation activity are compared.Wherein, when evaluating hydrogenation activity, as hydrogenation catalyst, make
2 weight %Pd/ silica 0.05g being dried used in 120 DEG C.
[table 3]
The ratio of 3. initialization solution of table and circulation reproduction operation solution turns
<separation of Anthraquinones>
Ethyl alcohol about 200mL is added in the distillate 32g of after-fractionating process to be cooled to room temperature after heating makes it dissolve
(recrystallization).It is dried after crystallization is separated by filtration.The distillate of following presentation after-fractionating process and by recrystallizing back
The composition of the crystallization of receipts.Anthraquinones can be separated with 64% rate of recovery from trioctyl phosphate and unknown ingredient.Using this method,
It can be recycled the Anthraquinones of recycling as the ingredient of working solution.
[table 4]
The composition of the distillate of 4. after-fractionating process of table and the crystallization by recrystallization recycling
Example 2
Implementing the first distillation process and after-fractionating process of the invention under different conditions with example 1, to initialization
Solution and circulation are compared with reproduction operation solution.
<the first distillation process>
Working solution 351g is added in the 500mL flask that distilling apparatus has.It is distilled under reduced pressure, vacuum degree
Always it controls in 1.3kPa.Temperature in flask is from room temperature to 157 DEG C.Persistently carry out distillation until finally 1.3kPa,
Distillate is no longer distilled out under conditions of 157 DEG C.
<after-fractionating process>
Residue obtained in the first distillation process is distilled under the pressure lower than the first distillation process.Vacuum degree exists
It distills and is changed between a period of time inherence 10Pa~150Pa started, it is final to stablize in 0.01kPa~0.04kPa.In flask
Temperature from room temperature to 181 DEG C.Distillation is persistently carried out until finally no longer distilling out under conditions of 0.01kPa, 181 DEG C
Distillate.
<distillation result>
The composition of initialization solution and the distillate, residue that are recycled by each distillation process is shown in table 5.
[table 5]
The composition (material balance) of 5. initialization solution of table and distillate, residue
According to method same as Example 1, thick reproduction operation solution is prepared.Table 6 indicates initialization solution and thick regeneration work
Make the composition of solution.
[table 6]
The composition of table 6. initialization solution and thick reproduction operation solution
By cleaning process same as example 1, circulation reproduction operation solution is prepared.Table 7 indicate initialization solution with
The comparison of the density, viscosity, hydrogenation activity of circulation reproduction operation solution.Wherein, it when evaluating hydrogenation activity, is urged as hydrogenation
Agent uses 1 weight %Pd/ silica alumina 0.1g being dried at 120 DEG C.
[table 7]
7. initialization solution of table is compared with recycling with reproduction operation solution
Example 3
Implementing the first distillation process and after-fractionating process of the invention under different conditions with example 1,2, to initial work
Make solution and circulation to be compared with reproduction operation solution.
<the first distillation process>
Working solution 351g same as Example 2 is added in the 500mL flask that distilling apparatus has.It carries out under reduced pressure
Distillation, vacuum degree are controlled always in 1.3kPa.Temperature in flask is from room temperature to 180 DEG C.Distillation is persistently carried out until most
Distillate is no longer distilled out under conditions of 1.3kPa, 180 DEG C eventually.
<after-fractionating process>
Residue obtained in the first distillation process is distilled under the pressure lower than the first distillation process.Vacuum degree begins
Control is in 0.13kPa eventually.Temperature in flask is from room temperature to 250 DEG C.Persistently carry out distillation until finally 0.13kPa,
Distillate is no longer distilled out under conditions of 250 DEG C.<distillation result>
The composition of initialization solution and the distillate, residue that are recycled by each distillation process is shown in table 8.
[table 8]
The composition (material balance) of 8. initialization solution of table and distillate, residue
According to method same as Example 1, thick reproduction operation solution is prepared.Table 9 indicates initialization solution and thick regeneration work
Make the composition of solution.
[table 9]
The composition of table 9. initialization solution and thick reproduction operation solution
By cleaning process same as example 1, circulation reproduction operation solution is prepared.Table 10 indicates density, viscosity plus hydrogen
Active comparison.Wherein, when evaluating hydrogenation activity, as hydrogenation catalyst, 1 weight % being dried at 120 DEG C is used
Pd/ silica alumina 0.1g.
[table 10]
The evaluation of reproduction operation solution of 10. initialization solution of table and circulation
Example 4
Thick reproduction operation solution obtained in example 2 is cleaned 2 times with the pure water of 2 times of volumes, obtains circulation regeneration work
Make solution (pure water cleaning).According to method same as Example 2, implement hydrogenation activity test.Hydrogenation catalyst use 120 DEG C into
1 dry weight %Pd/ silica alumina 0.1g of row.Table 11 indicates the result of hydrogenation activity test.Pure water is only carried out
The circulation of cleaning is higher than initialization solution with the hydrogenation activity of reproduction operation solution, but has carried out the circulation regeneration of alkali cleaning
The hydrogenation activity of working solution (example 2) is higher.
[table 11]
11. hydrogenation activity of table
Claims (16)
1. a kind of peroxidating method for preparing hydrogen characterized by comprising
Hydrogen peroxide manufacturing process carries out oxygen after hydrogenating containing the working solution of aromatic hydrocarbon, trioctyl phosphate and Anthraquinones
Change, thus generates hydrogen peroxide, the hydrogen peroxide is extracted from working solution, the working solution after extracting the hydrogen peroxide returns to
In hydrogenation process, recycled；
Step for regeneration of working solution, by the inert matter generated with the generation of the hydrogen peroxide as by-product from described
It is removed in working solution, prepares the thick reproduction operation solution after the inert matter is removed；With
Circulation reproduction operation solution preparation section carries out alkali cleaning, preparation circulation regeneration to the thick reproduction operation solution
Working solution,
The step for regeneration of working solution includes:
I) pass through the first distillation process of the distillation recovery aromatic hydrocarbon carried out under atmospheric pressure or atmospheric pressure pressure below；With
Ii) then by much lower pressure and 160 DEG C or more be distilled to recover Anthraquinones and trioctyl phosphate the carried out
Two distillation process.
2. peroxidating method for preparing hydrogen as described in claim 1, it is characterised in that:
Pressure in first distillation process is in the range of 1kPa~100kPa.
3. peroxidating method for preparing hydrogen as claimed in claim 1 or 2, it is characterised in that:
Pressure in the after-fractionating process is in 1kPa or less.
4. peroxidating method for preparing hydrogen according to any one of claims 1 to 3, it is characterised in that:
Temperature in the after-fractionating process is in the range of 160 DEG C~300 DEG C.
5. peroxidating method for preparing hydrogen as described in any one of claims 1 to 4, it is characterised in that:
The Anthraquinones include alkyl-anthraquinone and alkyl tetrahydro anthraquinone.
6. such as peroxidating method for preparing hydrogen according to any one of claims 1 to 5, it is characterised in that:
Including circulation reproduction operation solution is returned to the process in hydrogen peroxide manufacturing process.
7. peroxidating method for preparing hydrogen as claimed in claim 6, it is characterised in that:
The solvent ratio of components of the thick reproduction operation solution is relative to the working solution recycled in hydrogen peroxide manufacturing process
Solvent ratio of components is in the range of ± 20 percentage point.
8. peroxidating method for preparing hydrogen as claimed in claims 6 or 7, it is characterised in that:
The concentration of Anthraquinones in the thick reproduction operation solution is in the working solution recycled in hydrogen peroxide manufacturing process
Anthraquinones concentration more than and the saturated concentration of Anthraquinones below range in.
9. the peroxidating method for preparing hydrogen as described in any one of claim 6~8, it is characterised in that:
In the circulation in reproduction operation solution preparation section, reproduction operation solution be adjusted to saturated water component 20%~
160%.
10. the peroxidating method for preparing hydrogen as described in any one of claim 6~9, it is characterised in that:
The circulation work that reproduction operation solution preparation section further includes that the reproduction operation solution after cleaning to alkali is washed
Sequence.
11. such as peroxidating method for preparing hydrogen according to any one of claims 1 to 10, it is characterised in that:
It further include the process of separating anthraquinone and trioctyl phosphate from the distillate of the after-fractionating process.
12. peroxidating method for preparing hydrogen as claimed in claim 11, it is characterised in that:
The process of the separating anthraquinone and trioctyl phosphate is carried out using recrystallization.
13. a kind of hydrogen peroxide manufacture system, for destilling tower, preparation vessel, rinse bath, hydrogenation tower, oxidizing tower and extraction
The hydrogen peroxide manufacture system of tower, the hydrogen peroxide manufacture system are characterized in that:
There is destilling tower unknown ingredient discharge pipe, destilling tower and preparation vessel to distill distillate supply pipeline and back segment by leading portion
The connection of distillate supply pipeline is distilled, preparation vessel is connected to rinse bath by thick reproduction operation solution feed line, and rinse bath connects
It is connected to aqueous slkali supply pipeline and water supplying pipe line, rinse bath has waste liquid pipeline, and rinse bath and hydrogenation tower are by recycling with again
Raw working solution supply pipeline connection, hydrogenation tower are connected with hydrogenant agent supply pipeline, hydrogenate tower and oxidizing tower passes through hydrogenated work
Solution feed line connection, oxidizing tower are connected with oxidant supply pipeline, oxidizing tower and extraction column and are supplied by oxidation working solution
It is connected to pipeline, there is extraction column hydrogen peroxide feed-line, destilling tower and extraction column to pass through the work after hydrogen peroxide extraction
The supply pipeline of solution is connected to.
14. system as claimed in claim 13, it is characterised in that:
Also there is leading portion to distill distillate tank, destilling tower and leading portion distillation distillate tank and pass through leading portion distillation distillate feed-line
Connection, leading portion distill distillate tank and are connected to preparation vessel by leading portion distillation distillate supply pipeline.
15. system as claimed in claim 13, it is characterised in that:
Also there is back segment to distill distillate tank, destilling tower and back segment distillation distillate tank and pass through back segment distillation distillate feed-line
Connection, back segment distill distillate tank and are connected to preparation vessel by back segment distillation distillate supply pipeline.
16. system as claimed in claim 13, it is characterised in that:
Also there is recrystallization slot, recrystallization slot has filter and waste liquid pipeline, and recrystallization slot is connected with recrystallization solvent supply
Pipeline, recrystallization slot and destilling tower distill distillate supply pipeline by back segment and are connected to, and recrystallize slot and preparation vessel passes through anthraquinone
The connection of class supply pipeline.
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| CN112499595A (en) * | 2020-11-30 | 2021-03-16 | 平湖石化有限责任公司 | Production process of multi-component full-acidic fixed bed hydrogen peroxide |
| CN112919425A (en) * | 2021-02-03 | 2021-06-08 | 安徽金禾实业股份有限公司 | Method for circulating filtration in hydrogen peroxide production |
| CN114506820A (en) * | 2022-03-18 | 2022-05-17 | 西安吉利电子新材料股份有限公司 | Method for directly producing electronic grade hydrogen peroxide from hydrogen and oxygen |
| WO2024059990A1 (en) * | 2022-09-20 | 2024-03-28 | The University Of British Columbia | Methods and apparatus for indirect production of hydrogen peroxide using amyl-anthraquinone for hydrogen transport |
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| CN113371744A (en) * | 2021-06-04 | 2021-09-10 | 刘�文 | Waste activated alumina treatment process |
Also Published As
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| JP6972802B2 (en) | 2021-11-24 |
| JP2019048740A (en) | 2019-03-28 |
| CN208964546U (en) | 2019-06-11 |
| TW201912567A (en) | 2019-04-01 |
| KR102617500B1 (en) | 2023-12-22 |
| TWI770262B (en) | 2022-07-11 |
| CN117105178A (en) | 2023-11-24 |
| KR20190028289A (en) | 2019-03-18 |
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