CN117105178A - Method for producing hydrogen peroxide - Google Patents
Method for producing hydrogen peroxide Download PDFInfo
- Publication number
- CN117105178A CN117105178A CN202311078146.3A CN202311078146A CN117105178A CN 117105178 A CN117105178 A CN 117105178A CN 202311078146 A CN202311078146 A CN 202311078146A CN 117105178 A CN117105178 A CN 117105178A
- Authority
- CN
- China
- Prior art keywords
- working solution
- distillation
- hydrogen peroxide
- tank
- distillate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 314
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 135
- 239000012224 working solution Substances 0.000 claims abstract description 332
- 238000004821 distillation Methods 0.000 claims abstract description 263
- 230000008929 regeneration Effects 0.000 claims abstract description 126
- 238000011069 regeneration method Methods 0.000 claims abstract description 126
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 118
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 73
- 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 abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 58
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 46
- 238000005406 washing Methods 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000004064 recycling Methods 0.000 claims abstract description 26
- 239000006227 byproduct Substances 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000001953 recrystallisation Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000003513 alkali Substances 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 46
- 238000012546 transfer Methods 0.000 claims description 43
- 238000004140 cleaning Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 31
- 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 28
- 238000000605 extraction Methods 0.000 claims description 28
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- 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 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 230000000694 effects Effects 0.000 description 21
- 239000002798 polar solvent Substances 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- -1 pulp Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000001172 regenerating effect Effects 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000706 filtrate 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
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000011084 recovery Methods 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
- 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 4
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- IMXBRVLCKXGWSS-UHFFFAOYSA-N methyl 2-cyclohexylacetate Chemical compound COC(=O)CC1CCCCC1 IMXBRVLCKXGWSS-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 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 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 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
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-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
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- NSHCRPPLVZTBPG-UHFFFAOYSA-N anthracene;phenol Chemical class OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC2=CC3=CC=CC=C3C=C21 NSHCRPPLVZTBPG-UHFFFAOYSA-N 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
- 230000008901 benefit Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- ADHYTCPJVXOAJX-UHFFFAOYSA-N 1,3-dimethylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3C(=O)C2=C1 ADHYTCPJVXOAJX-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
- 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
- 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
- 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 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
- 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
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- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
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- 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
- 125000003118 aryl group Chemical group 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical class CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 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
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 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
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- ZJQPLBFKBQYYIO-UHFFFAOYSA-N dodecasodium;trisilicate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] ZJQPLBFKBQYYIO-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 238000004817 gas chromatography 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
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000037081 physical activity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 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
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate 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
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 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
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 238000003756 stirring Methods 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
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000003809 water extraction 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 method for removing inactive substances from a working solution containing trioctyl phosphate (TOP) to obtain a high-quality regenerated working solution. A method for producing hydrogen peroxide comprises: a hydrogen peroxide production step of hydrogenating and oxidizing a working solution containing aromatic hydrocarbons, TOP and anthraquinones to produce hydrogen peroxide, extracting the hydrogen peroxide from the working solution, and returning the working solution after extracting the hydrogen peroxide to the hydrogenation step cycle; a working solution regeneration step of removing inactive substances, which are by-products associated with the production of hydrogen peroxide, from the working solution to prepare a crude regenerated working solution; and a step of alkali-washing the crude regeneration working solution to prepare a regeneration working solution for recycling, wherein the working solution regeneration step comprises: i) A first distillation step of recovering aromatic hydrocarbons by distillation performed at atmospheric pressure or lower; ii) a second distillation step of recovering anthraquinones and TOP by distillation performed at a lower pressure and 160 ℃ or higher.
Description
The application date is09/06 of 2018Application number is201811036580.4The patent application entitled "method for producing hydrogen peroxide" is filed herewith.
Technical Field
The present invention relates to a method for producing hydrogen peroxide using anthraquinones, and more particularly to a method for producing hydrogen peroxide including a step of regenerating a working solution.
Background
Hydrogen peroxide has an oxidizing ability and a strong bleaching and sterilizing action, and is therefore used as a bleaching agent, a sterilizing agent, etc. for paper, pulp, fiber, etc. The decomposition products of hydrogen peroxide are water and oxygen, and thus are also important from the viewpoint of green chemistry, and particularly, have been attracting attention as a substitute for chlorine-based bleaching agents. In addition, the amount of hydrogen peroxide used in semiconductor industries such as surface cleaning of semiconductor substrates and the like, chemical polishing of copper, tin and other copper alloy surfaces, etching of electronic circuits and the like is also increasing. Further, hydrogen peroxide is widely used in oxidation reactions typified by epoxidation and hydroxylation, and is an important industrial product.
As an industrial method for producing hydrogen peroxide, the anthraquinone method is known. In this method, anthraquinones are dissolved in an organic solvent to obtain a working solution, and in a hydrogenation step, the anthraquinones are hydrogenated in the presence of a hydrogenation catalyst to produce anthracenediphenols. Then, in the oxidation step, the anthracene diphenols are converted into anthraquinones again, and hydrogen peroxide is produced. Hydrogen peroxide in the working solution is separated from the working solution by water extraction or the like. The working solution after hydrogen peroxide extraction is returned to the hydrogenation step again to form a cyclic process.
In the process of repeating the operation of producing hydrogen peroxide by hydrogenating anthraquinones contained in the working solution to anthracenediphenols and oxidizing them to anthraquinones, a tetrahydroanthraquinone epoxide, a tetrahydroxyanthrone, a hydroxyanthrone, an anthraquinone monomer by-product such as anthrone, a solvent adduct of anthraquinones, and a polymer of anthraquinones, which do not contribute to the production of hydrogen peroxide, are produced. Degradation products of the solvent component are also generated. Such components that are not related to the production of hydrogen peroxide are classified as "inactive substances". This increase in inactive material causes a decrease in the concentration of the active material anthraquinone, and the like, and decreases the capability of each step of the circulation process. Therefore, a working solution having a low concentration of an inactive substance and capable of maintaining a sufficiently high concentration of an active substance is demanded (patent document 1).
Prior art literature
Patent literature
Patent document 1: WO2007/129769
Disclosure of Invention
Technical problem to be solved by the invention
The composition of the working solution varies depending on the hydrogen peroxide production facility, but a working solution containing an aromatic hydrocarbon as a nonpolar solvent, tris (2-ethylhexyl) phosphate (CAS number: 78-42-2, hereinafter sometimes referred to as "trioctyl phosphate" or "TOP") as a polar solvent, and alkylanthraquinone and alkyltetrahydroanthraquinone as anthraquinones is often used. However, in a working solution containing trioctyl phosphate as a polar solvent, a method for suppressing the concentration of an inactive substance and maintaining the concentration of an active substance in a sufficiently high state has not been reported so far. Accordingly, an object of the present invention is to provide a method for removing an inactive substance from a working solution containing trioctyl phosphate, which is used in the production of hydrogen peroxide by the anthraquinone process, and for maintaining or improving the physical properties and/or activity of the working solution.
Technical scheme for solving technical problems
As a result of intensive studies to solve the above problems, the inventors of the present invention have found a method for removing by-products from a working solution containing aromatic hydrocarbons, trioctyl phosphate and anthraquinones. In this method, aromatic hydrocarbons are recovered by distillation performed at atmospheric pressure or below, anthraquinone and trioctyl phosphate are recovered by distillation performed at 160 ℃ or above at a lower pressure, and the whole distillate recovered is reused as a working solution. Further, the present inventors have further studied and found that the hydrogenation activity is improved by alkali-washing the regenerated working solution.
One aspect of the invention is as follows.
[1] A method for producing hydrogen peroxide, comprising:
a hydrogen peroxide production step of hydrogenating and oxidizing a working solution containing an aromatic hydrocarbon, trioctyl phosphate and anthraquinones to produce hydrogen peroxide, extracting the hydrogen peroxide from the working solution, and returning the working solution after extracting the hydrogen peroxide to the hydrogenation step to circulate the working solution;
a working solution regeneration step of removing an inactive substance produced as a by-product in association with the production of hydrogen peroxide from the working solution to prepare a crude regenerated working solution from which the inactive substance has been removed; and
A process for preparing a recycling regenerated working solution, wherein the crude regenerated working solution is subjected to alkali cleaning to prepare the recycling regenerated working solution,
the working solution regeneration step includes:
i) A first distillation step of recovering aromatic hydrocarbons by distillation performed at atmospheric pressure or below; and
ii) a second distillation step of recovering anthraquinones and trioctyl phosphate by distillation at a lower pressure and 160 ℃ or higher.
[2] The method for producing hydrogen peroxide according to [1], wherein the pressure in the first distillation step is in the range of 1kPa to 100 kPa.
[3] The method for producing hydrogen peroxide according to [1] or [2], wherein the pressure in the second distillation step is 1kPa or less.
[4] The method for producing hydrogen peroxide according to any one of [1] to [3], wherein the temperature in the second distillation step is in the range of 160℃to 300 ℃.
[5] The method for producing hydrogen peroxide according to any one of [1] to [4], wherein the anthraquinones include alkylanthraquinone and alkyltetrahydroanthraquinone.
[6] The method for producing hydrogen peroxide according to any one of [1] to [5], wherein the method comprises a step of returning the recycling regeneration working solution to the hydrogen peroxide production step.
[7] The method for producing hydrogen peroxide according to [6], wherein the solvent composition ratio of the crude regeneration working solution is within a range of.+ -. 20% relative to the solvent composition ratio of the working solution circulated in the hydrogen peroxide production process.
[8] The method for producing hydrogen peroxide according to [6] or [7], wherein the concentration of the anthraquinones in the crude regeneration working solution is in a range of not less than the concentration of the anthraquinones in the working solution circulated in the hydrogen peroxide production step and not more than the saturation concentration of the anthraquinones.
[9] The method for producing hydrogen peroxide according to any one of [6] to [8], wherein in the step of producing the recycling regeneration working solution, the regeneration working solution is adjusted to 20% to 160% of the saturated water content.
[10] The method for producing hydrogen peroxide according to any one of [6] to [9], wherein the step of producing the recycling regenerated working solution further comprises a step of washing the regenerated working solution after alkali washing.
[11] The method for producing hydrogen peroxide according to any one of [1] to [10], further comprising a step of separating anthraquinone and trioctyl phosphate from the distillate of the second distillation step.
[12] The method for producing hydrogen peroxide according to [11], wherein the step of separating anthraquinone from trioctyl phosphate is performed by recrystallization.
[13] A hydrogen peroxide production system having a distillation column, a production tank, a cleaning tank, a hydrogenation column, an oxidation column, and an extraction column, wherein,
the distillation tower has an unknown component discharge line, the distillation tower and the preparation tank are communicated through a front-stage distillation distillate supply line and a rear-stage distillation distillate supply line, the preparation tank and the cleaning tank are communicated through a crude regeneration working solution supply line, the cleaning tank is connected with an alkali solution supply line and a water supply line, the cleaning tank has a waste liquid line, the cleaning tank and the hydrogenation tower are communicated through a regeneration working solution supply line for circulation, the hydrogenation tower is connected with a hydrogenating agent supply line, the hydrogenation tower and the oxidation tower are communicated through a hydrogenation working solution supply line, the oxidation tower is connected with an oxidizing agent supply line, the oxidation tower and the extraction tower are communicated through an oxidation working solution supply line, the extraction tower has a hydrogen peroxide delivery line, and the distillation tower and the extraction tower are communicated through a supply line of working solution after hydrogen peroxide extraction.
[14] The system of [13], wherein there is further provided a front-stage distillation distillate tank, the distillation column and the front-stage distillation distillate tank being in communication via a front-stage distillation distillate transfer line, the front-stage distillation distillate tank and the production tank being in communication via a front-stage distillation distillate supply line.
[15] The system of [13], wherein there is further provided a post-stage distillation distillate tank, the distillation column and the post-stage distillation distillate tank being in communication via a post-stage distillation distillate transfer line, the post-stage distillation distillate tank and the production tank being in communication via a post-stage distillation distillate supply line.
[16] The system according to [13], wherein the system further comprises a recrystallization tank having a filter and a waste liquid line, wherein the recrystallization tank is connected to a recrystallization solvent supply line, wherein the recrystallization tank and the distillation column are connected by a post-distillation distillate supply line, and wherein the recrystallization tank and the production tank are connected by an anthraquinone supply line.
Effects of the invention
The present invention can achieve the following 1 or more effects.
(1) The inactive material can be removed from the working solution containing trioctyl phosphate as a polar solvent, in which the inactive material is accumulated.
(2) Anthraquinone as an active material can be efficiently recovered from a working solution containing trioctyl phosphate as a polar solvent and reused.
(3) By reducing the amount of inactive substances in the circulating working solution, the efficiency of each step in the production of hydrogen peroxide can be kept high.
(4) The viscosity of the circulating working solution can be maintained at a low level.
(5) The hydrogenation activity of the circulating working solution can be maintained at a high state.
(6) The method can be applied to a working solution containing trioctyl phosphate with high use frequency, so that the method has wide application range and can be expected to make a great contribution to the efficiency of hydrogen peroxide production.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a hydrogen peroxide production system of the present invention.
FIG. 2 is a schematic diagram of one embodiment of the hydrogen peroxide production system of the present invention having a recrystallization tank.
Symbol description
1: a distillation column; 2: a preparation groove; 3: a cleaning tank; 4: a hydrogenation tower; 5: an oxidation tower; 6: an extraction tower; 7: a distillate transfer line; 7a: a front-end distillate transfer line; 7b: a post distillation distillate transfer line; 7c: distilling off the TOP transfer line; 7d: distilling off the recrystallization solvent delivery line; 8: an unknown component discharge line; 9: a front-end distillation distillate tank; 10: a post distillation distillate tank; 11: a front-end distillate feed line; 12: a post distillation distillate supply line; 13: a crude regeneration working solution supply line; 14: an alkali solution supply line; 15: a water supply line; 16: a recycle regeneration working solution supply line; 17: a waste liquid line; 18: a hydrogenating agent recycle line; 19: a hydrogenating agent supply line; 20: a hydrogenation working solution supply line; 21: an oxidant supply line; 22: an exhaust line; 23: an oxidation working solution supply line; 24: a water supply line; 25: a hydrogen peroxide delivery line; 26: a supply line for the working solution after hydrogen peroxide extraction; 27: a circulation line for the working solution after hydrogen peroxide extraction; 28: an unknown component; 29: an alkaline solution; 30: water; 31: waste liquid; 32: a hydrogenating agent; 33: an oxidizing agent; 34: unreacted oxidant; 35: water; 36: hydrogen peroxide water; 37: a recrystallization tank; 38: a recrystallization solvent tank; 39: a recrystallization solvent feed line; 40: anthraquinone type supply lines; 41: a waste liquid line; 42: a filtrate transfer line; v: and a valve.
Detailed Description
One embodiment of the present invention relates to a method for producing hydrogen peroxide (hereinafter, sometimes referred to as "the method for producing hydrogen peroxide of the present invention"), comprising:
a hydrogen peroxide production step of hydrogenating (reducing) a working solution containing an aromatic hydrocarbon, trioctyl phosphate and anthraquinones and then oxidizing the working solution to produce hydrogen peroxide, extracting the hydrogen peroxide from the working solution, and returning the working solution after extracting the hydrogen peroxide to the hydrogenation step to circulate the working solution;
a working solution regeneration step of removing an inactive substance produced as a by-product in association with the production of hydrogen peroxide from the working solution to prepare a crude regenerated working solution from which the inactive substance has been removed; and
a process for preparing a recycling regenerated working solution, wherein the crude regenerated working solution is subjected to alkali cleaning to prepare the recycling regenerated working solution,
the working solution regeneration step includes:
i) A first distillation step of recovering aromatic hydrocarbons by distillation performed at atmospheric pressure or below; and
ii) a second distillation step of recovering anthraquinones and trioctyl phosphate by distillation at a lower pressure and 160 ℃ or higher.
The aromatic hydrocarbon contained in the working solution is not limited, and examples thereof include aromatic hydrocarbons substituted with at least 1 alkyl group, particularly alkylbenzenes having 8, 9,10, 11 or 12 carbon atoms (for example, trimethylbenzene having 9 carbon atoms, etc.), and mixtures thereof, and the like, and preferably compounds capable of dissolving anthraquinone are mentioned. In a particular embodiment, the aromatic hydrocarbon is selected from the group consisting of mixed solvents having 10 carbon atoms and mixed solvents having 9 carbon atoms (e.g., isopropyl benzene isomer mixtures). Trioctyl phosphate as a polar solvent is a compound having the following structure.
The anthraquinones contained in the working solution contain at least 1 of anthraquinone (9, 10-anthracenedione) capable of generating hydrogen peroxide by the anthraquinone process, tetrahydroanthraquinone, and derivatives thereof. The derivative of anthraquinone capable of generating hydrogen peroxide is not limited, and examples thereof include alkylanthraquinone. Alkylanthraquinone means anthraquinone substituted with at least 1 alkyl group. In a particular embodiment, alkylanthraquinone includes anthraquinones substituted in at least one of the 1, 2 or 3 positions with a linear or branched aliphatic substituent containing at least 1 carbon atom. The alkyl substituents in the alkylanthraquinone preferably contain 1 to 9, more preferably 1 to 6 carbon atoms. Specific examples of the alkylanthraquinone include, but are not limited to, methylanthraquinone (2-methylanthraquinone and the like), dimethylanthraquinone (1, 3-dimethylanthraquinone, 2, 3-dimethylanthraquinone, 1, 4-dimethylanthraquinone, 2, 7-dimethylanthraquinone and the like), ethylanthraquinone (2-ethylanthraquinone and the like), propylanthraquinone (2-n-propylanthraquinone, 2-isopropylanthraquinone and the like), butylanthraquinone (2-sec-butylanthraquinone, 2-tert-butylanthraquinone and the like), pentynthraquinone (2-sec-pentynthraquinone, 2-tert-pentynthraquinone and the like) and the like. As the preferred alkylanthraquinone, ethylanthraquinone, pentynthraquinone or a mixture thereof may be mentioned. The concentration of the alkylanthraquinone in the working solution can be controlled according to the process conditions, and for example, the concentration range of the alkylanthraquinone is 0.4 to 1.0 mol/L.
The derivative of tetrahydroanthraquinone capable of generating hydrogen peroxide is not limited, and examples thereof include alkyl tetrahydroanthraquinones. Alkyl tetrahydroanthraquinone means tetrahydroanthraquinone substituted with at least 1 alkyl group. In a particular embodiment, the alkyl tetrahydroanthraquinones include tetrahydroanthraquinones substituted in at least one of the 1, 2, or 3 positions with a linear or branched aliphatic substituent having at least 1 carbon atom. The alkyl substituents in the alkyl tetrahydroanthraquinones preferably contain from 1 to 9, more preferably from 1 to 6, carbon atoms. Specific examples of the alkyl tetrahydroanthraquinone include, but are not limited to, methyl tetrahydroanthraquinone (2-methyl tetrahydroanthraquinone and the like), dimethyl tetrahydroanthraquinone (1, 3-dimethyl tetrahydroanthraquinone, 2, 3-dimethyl tetrahydroanthraquinone, 1, 4-dimethyl tetrahydroanthraquinone, 2, 7-dimethyl tetrahydroanthraquinone and the like), ethyl tetrahydroanthraquinone (2-ethyl tetrahydroanthraquinone and the like), propyl tetrahydroanthraquinone (2-n-propyl tetrahydroanthraquinone, 2-isopropyl tetrahydroanthraquinone and the like), butyl tetrahydroanthraquinone (2-sec-butyl tetrahydroanthraquinone, 2-tert-butyl tetrahydroanthraquinone and the like), amyl tetrahydroanthraquinone (2-sec-amyl tetrahydroanthraquinone, 2-tert-amyl tetrahydroanthraquinone and the like) and the like. As the preferred alkyltetrahydroanthraquinones, ethyltetrahydroanthraquinone, pentyltetrahydro anthraquinone or mixtures thereof may be mentioned.
In one embodiment, the working solution contains a combination of alkylanthraquinone and alkyltetrahydroanthraquinone. The molar ratio of the alkylanthraquinone to the alkyltetrahydroanthraquinone in the combination is not particularly limited, and is preferably 0.05:1 to 100:1, more preferably 0.1:1 to 75:1, and still more preferably 0.2:1 to 50:1, as expressed by alkylanthraquinone to alkyltetrahydroanthraquinone. The weight ratio of the alkylanthraquinone to the alkyltetrahydroanthraquinone is not particularly limited, and is preferably 0.05:1 to 100:1, more preferably 0.1:1 to 75:1, and still more preferably 0.2:1 to 50:1, as expressed by alkylanthraquinone to alkyltetrahydroanthraquinone. Particularly preferred combinations of alkylanthraquinone and alkyltetrahydroanthraquinone are combinations of ethylanthraquinone and ethylanthraquinone.
The hydrogen peroxide production process may be performed according to a known method for producing hydrogen peroxide by the anthraquinone process. The hydrogen peroxide production process typically includes a process of hydrogenating the working solution, a process of oxidizing the hydrogenated working solution, and a process of extracting hydrogen peroxide generated by the oxidation into an aqueous phase. The hydrogenation of the working solution may be performed, for example, by bubbling the working solution with a hydrogen-containing gas such as hydrogen gas or a mixture of an inert gas (nitrogen gas or the like) and hydrogen gas in the presence of a hydrogenation catalyst. The oxidation of the hydrogenated working solution can be performed, for example, by bubbling the working solution with an oxygen-containing gas such as air or oxygen. The extraction of hydrogen peroxide into the aqueous phase may be performed, for example, by mixing the oxidized working solution with water, separating the aqueous phase, and the like. The extracted hydrogen peroxide may then be subjected to refining, concentration, and the like.
The removal of the inactive substances from the working solution in the working solution regeneration step is performed by a distillation step including:
i) A first distillation step (hereinafter, also referred to as a former distillation step) of recovering aromatic hydrocarbons by distillation performed at atmospheric pressure or below; and
ii) a second distillation step (hereinafter, also referred to as a post-distillation step) of recovering anthraquinone and trioctyl phosphate by distillation at a lower pressure and 160 ℃ or higher.
In the first distillation step, the working solution is distilled at a pressure equal to or lower than atmospheric pressure, and aromatic hydrocarbons contained in the working solution are recovered as a distillate. The distillation pressure is not particularly limited as long as aromatic hydrocarbons can be recovered, and may be, for example, 0.5kPa to 100kPa, 0.8kPa to 100kPa, 1kPa to 50kPa, or the like. Preferably, the distillation pressure is such that aromatic hydrocarbons can be distilled, but trioctyl phosphate and anthraquinones are not distilled. The distillation temperature is not particularly limited as long as aromatic hydrocarbons can be recovered, and may be, for example, 110 to 240 ℃, 120 to 220 ℃, 130 to 200 ℃, 140 to 190 ℃, 150 to 185 ℃, or the like. The distillation temperature at which aromatic hydrocarbons can be distilled but trioctyl phosphate and anthraquinones are not distilled is preferable. From the viewpoint of recovery of aromatic hydrocarbons, the distillation in the first distillation step is preferably continued until the distillate is no longer distilled. The aromatic hydrocarbons distilled in the first distillation step are reused as components of the regeneration working solution.
The working solution supplied to the first distillation step is typically a working solution circulated in the hydrogen peroxide production step, and contains an inactive substance that is produced as a by-product along with the production of hydrogen peroxide. The working solution may be collected at any stage in the hydrogen peroxide production process, but from the viewpoint of safety, it is preferable that the working solution contains no hydrogen peroxide or even a small amount (for example, 0.35g/L or less) of the working solution after the extraction process. Examples of the inactive material include by-products (oxides, decomposed products, and the like) derived from anthraquinones or solvents (aromatic hydrocarbons and trioctyl phosphate). Examples of the by-products derived from anthraquinones include monomeric by-products derived from anthraquinones such as tetrahydroanthraquinone epoxide, tetrahydroxyanthrone, hydroxyanthrone and anthrone, solvent adducts of anthraquinones, and polymers of anthraquinones. Examples of the by-products derived from the solvent include carboxylic acids, polyols, phenols, and the like.
In the second distillation step, the residue obtained in the first distillation step is distilled at a pressure lower than that in the first distillation step and at 160 ℃ or higher, and anthraquinones and trioctyl phosphate are recovered as a distillate. This can remove by-products (high-boiling components) having a boiling point higher than that of anthraquinones and trioctyl phosphate. The distillation pressure is not particularly limited as long as it is a pressure at which anthraquinone and trioctyl phosphate can be recovered, and may be, for example, 0.001 to 1kPa, 0.002 to 0.5kPa, 0.005 to 0.2kPa, 0.008 to 0.1kPa, 0.1 to 0.3kPa, or the like. Preferably, the distillation pressure is a distillation pressure at which anthraquinone and trioctyl phosphate are distilled off, but the distillation of by-products is small. The distillation temperature is not particularly limited as long as it is a temperature at which anthraquinones and trioctyl phosphate can be recovered, and may be 160 to 300 ℃, 165 to 280 ℃, 170 to 270 ℃, 175 to 260 ℃, 220 to 260 ℃, or the like. In some embodiments, the upper limit of the distillation temperature in the second distillation step may be less than 200 ℃. Thus, the first and second substrates are bonded together, the distillation temperature in the second distillation step in this embodiment may be, for example, 160℃to 199℃to 160℃to 198℃to 160℃to 197℃to 160℃to 196℃to 160℃to 195℃to 160℃to 194℃to 160℃to 193℃to 160℃to 192℃to 160℃to 191℃to 160℃to 190℃to 160℃to 189℃to 160℃to 188℃to 160℃to 187℃to 160℃to 186℃to 160℃to 185℃to 160℃to 183℃to 160℃to 182℃to 160℃to 181℃to 180 ℃. Preferably, the distillation temperature is a distillation temperature at which anthraquinone and trioctyl phosphate are distilled off, but the distillation of by-products is small.
From the viewpoint of recovery of anthraquinones, the distillation in the second distillation step is preferably continued until the distillate is no longer distilled. The average residence time in the second distillation step is not particularly limited, and may be, for example, 1 hour or more. The "residence time" means the time from the start to the stop of distillation or residue in the distillation step, and the "average residence time" means the simple arithmetic average of residence time when the same distillation step is performed 2 or more times. The average residence time in the second distillation step may be, for example, 1 to 10 hours, 6 to 10 hours, or the like. By setting the average residence time to 1 hour or more, the following advantages are obtained: recovery of anthraquinones increases, and conversion of by-products from anthraquinones to anthraquinones having hydrogen peroxide-generating ability occurs, and the amount of anthraquinones having hydrogen peroxide-generating ability increases. For example, a tetrahydroanthraquinone epoxide as a by-product can be converted to tetrahydroanthraquinone with hydrogen peroxide generating capability.
The anthraquinones and trioctyl phosphate distilled in the second distillation step are reused as components of the regeneration working solution.
The apparatus used in the distillation step is not particularly limited as long as it can perform distillation at a predetermined temperature and pressure, and examples thereof include a batch distillation apparatus, a continuous distillation apparatus, a thin film distillation apparatus, and the like. From the viewpoint of cost and the like, a distillation apparatus that can be used for both the first distillation step and the second distillation step is preferable.
In one embodiment, the method for producing hydrogen peroxide of the present invention further comprises a step of separating anthraquinone and trioctyl phosphate from the distillate of the second distillation step. The separation of the anthraquinones from trioctyl phosphate may be performed by recrystallising the anthraquinones. The recrystallization of the anthraquinones can be performed by heating and dissolving the anthraquinones in a recrystallization solvent and then cooling. After recrystallization, the recrystallized anthraquinones can be recovered and reused. Trioctyl phosphate separated from the anthraquinones can be reused by separation from the recrystallization solvent by distillation or the like. As the recrystallization solvent, a solvent having a large difference between the solubility of anthraquinones upon heating and the solubility upon cooling is preferable. Examples of the recrystallization solvent include alcohol solvents (for example, lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol, and 2-ethylhexanol), nonpolar solvents (for example, aromatic hydrocarbons) used as components of the working solution, and polar solvents (for example, TOP, diisobutylmethanol, tetrabutylurea, and methylcyclohexyl acetate). The recrystallization solvent may be composed of a single solvent or may be a mixture of a plurality of solvents. The amount of the recrystallization solvent to the working solution is preferably an amount in which the recrystallization of the anthraquinones can be favorably performed, and for example, may be 1 to 20 times, 2 to 15 times, 3 to 10 times, 4 to 8 times, or the like in terms of the volume (e.g., g/mL) of the solvent per unit weight of the working solution. By including a step of separating the anthraquinones from trioctyl phosphate, the anthraquinones can be recovered in a form of higher purity. Therefore, the concentration of by-products contained in the regeneration working solution can be further reduced.
The crude regeneration working solution in the working solution regeneration step can be prepared by mixing the aromatic hydrocarbon recovered in the first distillation step with the anthraquinone and trioctyl phosphate recovered in the second distillation step. In the mode including the step of separating the anthraquinones and trioctyl phosphate from the distillate of the second distillation step, the crude regeneration working solution may be prepared by mixing the aromatic hydrocarbon recovered in the first distillation step with the anthraquinones and trioctyl phosphate separately recovered after the second distillation step. In the present specification, the crude regeneration working solution means a regeneration working solution before alkali washing, which contains aromatic hydrocarbons, trioctyl phosphate and anthraquinones recovered in the distillation step.
When the solvent composition ratio in the working solution is changed, the density, viscosity, partition coefficient, and the like of the working solution are also changed. When these parameters are changed, the operating conditions and facilities of each step also need to be changed, which is not preferable from the viewpoint of stable production of hydrogen peroxide. Therefore, the solvent composition ratio of the regenerated working solution is preferably adjusted to a value close to that of the working solution in the circulation process. For example, the solvent composition ratio (%) of the regenerated working solution is preferably adjusted to be within ±20%, preferably within ±10%, more preferably within ±5% of the working solution of the circulation process (however, the total of the adjusted solvent composition ratios does not exceed 100%). That is, when the solvent of the working solution is composed of aromatic hydrocarbon and trioctyl phosphate, and the solvent composition ratio (volume ratio) in the circulation process is such that the aromatic hydrocarbon is 70%:30%, it is desirable to adjust the solvent composition ratio of the regeneration working solution to 90%:10% to 50%:50%, preferably 80%:20% to 60%:40%, more preferably 75%:25% to 65%:35%.
In actual facilities, since the concentration of anthraquinones in the working solution in the circulation process has been reduced over the years, the operation is performed while new anthraquinones are appropriately replenished. In order not to decrease the concentration of the anthraquinones in the circulation process, it is also preferable to prepare the regeneration working solution so that the concentration of the anthraquinones in the circulation process is the same as that in the circulation process, or so that the concentration of the anthraquinones in the circulation process is not lower than the saturation concentration of the anthraquinones. For example, in the working solution containing an aromatic hydrocarbon, trioctyl phosphate, ethyl anthraquinone and ethyl tetrahydroanthraquinone, the preparation is preferably carried out such that the total concentration of ethyl anthraquinone and ethyl tetrahydroanthraquinone in the regenerated working solution is 0.1 to 1.4mol/L, preferably 0.3 to 1.2mol/L, more preferably 0.5 to 1.0 mol/L.
In the preparation of the crude regeneration working solution, 1 or 2 or more of aromatic hydrocarbons, trioctyl phosphate and anthraquinones from other sources may be mixed in addition to the components recovered in the distillation step. In particular embodiments, aromatic hydrocarbons, trioctyl phosphate, and/or anthraquinones from other sources include commercially available or newly synthesized materials.
In the regeneration working solution preparation step for circulation, the crude regeneration working solution obtained in the working solution regeneration step is subjected to alkali cleaning to prepare the regeneration working solution for circulation. By recycled regeneration working solution is meant a regeneration working solution after alkaline cleaning that is particularly suitable for use in a recycling process.
The alkaline washing may be performed by washing the crude regeneration working solution with an aqueous alkali solution or the like. The alkali contained in the aqueous alkali solution is preferably an alkali metal. The alkali metal used in the cleaning may be an alkali metal of group IA of the periodic table of elements, preferably lithium, sodium or potassium. The reagent containing these is not particularly limited, and examples thereof include lithium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium borate, sodium pyrophosphate, sodium metaborate, sodium nitrite, sodium perborate, sodium hydrogen phosphate, sodium silicate, sodium disilicate, sodium trisilicate, sodium stannate, sodium sulfide, sodium thiosulfate, sodium tungstate, potassium hydroxide, potassium borohydride, potassium carbonate, potassium cyanide, potassium nitrite, potassium phenolate, potassium hydrogen phosphate, potassium pyrophosphate, potassium stannate, and the like. The component contained in the aqueous alkali solution is preferably lithium hydroxide, sodium carbonate, sodium hydrogencarbonate or potassium hydroxide, more preferably sodium hydroxide, sodium carbonate, sodium hydrogencarbonate or potassium hydroxide, particularly preferably sodium hydroxide, sodium carbonate or sodium hydrogencarbonate. The pH of the alkali aqueous solution containing the alkali metal is preferably 8 or more, more preferably 10 or more, particularly preferably 12 or more.
The contact between the crude regeneration working solution and the aqueous alkali solution may be performed, for example, by contacting with an aqueous alkali solution in an amount of 0.2 times or more by volume relative to 1 part by volume of the crude regeneration working solution. The crude regeneration working solution is preferably contacted with 0.3 times or more by volume of an aqueous alkali solution. As a method of contact, a generally known mixing means can be used. For example, stirring, vibration, bubbling with an inert gas, a parallel flow contact method, a countercurrent contact method, and the like are mentioned, but the present invention is not limited to these, and any method is possible as long as the crude regeneration working solution can be effectively contacted with the aqueous alkali solution. In addition, the volume of the aqueous alkali to be contacted is not strictly limited, and may be appropriately selected depending on the apparatus in which the contact is performed and the operating conditions.
The contact time between the crude regeneration working solution and the aqueous alkali solution is, for example, 1 minute or more, more preferably 3 minutes or more, and particularly preferably 5 minutes or more, and may be appropriately selected depending on the apparatus in which the contact is performed and the operating conditions. The contact temperature of the crude regeneration working solution with the aqueous alkali solution is, for example, in the range of 0 to 70 ℃, preferably in the range of 10 to 60 ℃, and particularly preferably in the range of 20 to 50 ℃. The pressure in the contact treatment between the crude regeneration working solution and the aqueous alkali solution is not particularly limited, and is usually preferably kept at normal pressure. The aqueous alkali solution after the completion of the contact is separated from the crude regeneration working solution and discharged. The alkali washing may be performed 1 or more times, for example, 1, 2 or 3 or more times.
By alkali-washing the regeneration working solution, the hydrogenation activity of the regeneration working solution can be improved as compared with the case of washing with only water. In addition, when the crude regeneration working solution contains acidic impurities, the alkaline cleaning has an advantage that the acidic impurities can be removed.
In one embodiment, in the process of producing the recycling regeneration working solution, the water content of the crude regeneration working solution is adjusted to 20% to 160% of the saturated water content. In the hydrogenation step in the hydrogen peroxide production step, the water content of the working solution is preferably about 50% to about 95% of the saturation concentration at the hydrogenation temperature. The crude regenerated working solution prepared from the distillate recovered in the distillation step tends to have a low water content and a low hydrogenation reaction rate. Therefore, the aqueous content of the regeneration working solution for circulation returned to the circulation process is preferably higher than that of the crude regeneration working solution. The water content of the regeneration working solution can be increased to a level near the saturated water content by washing the crude regeneration working solution with an aqueous alkali solution. When the desired moisture range cannot be achieved by alkali washing, the water content can be adjusted by dehydration treatment, water make-up, washing with water, or the like.
In the process of preparing the recycled regeneration working solution, the washing may be performed with water in addition to the alkali washing. The water used for washing is preferably distilled water, ion-exchanged water, or water purified by a reverse osmosis method or the like, and water purified by a method other than the above is also preferably used. As the water used for cleaning, pure water is particularly preferred. The washing with water may be performed in the same manner as the alkali washing, except that water is used as a washing medium. Therefore, the capacity of the aqueous solution to be used for the crude regeneration working solution, the method of contact with the crude regeneration working solution, the contact time, the contact temperature, the contact pressure, and the like are the same as those described above for the alkaline cleaning. The washing with water may be performed before the alkali washing, may be performed after the alkali washing, or may be performed both before the alkali washing and after the alkali washing. The washing with water may be performed 1 or more times, for example, 1, 2 or 3 or more times.
In the process of preparing the recycled regenerating working solution, a treatment using a regenerated catalyst for regenerating anthraquinones from by-products of anthraquinones may be performed in addition to the alkali cleaning. The treatment with the regenerated catalyst may be performed by passing the regenerated working solution before or after the alkali cleaning through a fixed bed or a fluidized bed to which the regenerated catalyst is added. In the case of using the liquid for 1 time, there is an insufficient condition, and thus it is preferable to circulate the liquid. As the regenerated catalyst, activated alumina or silica alumina is preferable, and activated alumina is more preferable. The surface area and particle diameter of the regenerated catalyst may be appropriately selected depending on the reaction conditions and apparatus, and are not particularly limited. The reaction temperature is preferably in the range of 0℃to 200℃and more preferably 50℃to 150 ℃. Further, since the reaction proceeds, hydroquinone is accumulated, and the progress of the partial regeneration reaction is delayed, it is preferable to oxidize hydroquinone by contact with oxygen or air during the circulation of the liquid. The hydrogen peroxide generated at this time may be purged stepwise.
In one embodiment, the method for producing hydrogen peroxide of the present invention includes a step of returning the recycling regeneration working solution to the hydrogen peroxide production step. The recycled regeneration working solution may be returned to 1 or more steps selected from the hydrogenation step, the oxidation step, and the extraction step included in the hydrogen peroxide production step. Here, returning to a certain process means returning to any stage from the stage of ending the process before the process to the stage of ending the process before the process. For example, returning the circulating regeneration working solution to the hydrogenation step means returning the circulating regeneration working solution to any stage (for example, an outlet of the extraction device or an inlet of the hydrogenation device) from the stage at which the extraction step is completed to the stage before the hydrogenation step is completed. In a specific embodiment, the recycle regeneration working solution is returned to the hydrogenation step. This method is advantageous in that it can effectively utilize the high hydrogenation activity of the recycled regeneration working solution. Specific examples of this embodiment include a method in which a circulating regeneration working solution is mixed with a circulating working solution immediately before a hydrogenation apparatus (hydrogenation column), and the resulting mixed solution is introduced into the hydrogenation apparatus. In another specific embodiment, the recycled regeneration working solution is returned to the oxidation step and/or the extraction step. This method is advantageous when the water content of the circulating regeneration working solution is low.
Another aspect of the present invention relates to a method for producing a regenerative working solution for circulation (hereinafter, sometimes referred to as "the method for producing a regenerative working solution for circulation" according to the present invention), comprising:
a working solution regeneration step of removing an inactive substance from a working solution for hydrogen peroxide production containing an aromatic hydrocarbon, trioctyl phosphate, anthraquinones, and the inactive substance produced as a by-product with the production of hydrogen peroxide, to prepare a crude regeneration working solution from which the inactive substance has been removed; and
a process for preparing a recycling regenerated working solution, wherein the crude regenerated working solution is subjected to alkali cleaning to prepare the recycling regenerated working solution,
the working solution regeneration step includes:
i) A first distillation step of recovering aromatic hydrocarbons by distillation performed at atmospheric pressure or below; and
ii) a second distillation step of recovering anthraquinones and trioctyl phosphate by distillation at a lower pressure and 160 ℃ or higher.
The characteristics of each step of the method for producing a recycled regenerated working solution of the present invention are the same as those of the corresponding step in the method for producing hydrogen peroxide of the present invention.
A further aspect of the present invention relates to a method for producing hydrogen peroxide (hereinafter, sometimes referred to as "the hydrogen peroxide production method a of the present invention"), comprising:
A hydrogen peroxide production step of hydrogenating and oxidizing a working solution containing an aromatic hydrocarbon, trioctyl phosphate and anthraquinones to produce hydrogen peroxide, extracting the hydrogen peroxide from the working solution, and returning the working solution after extracting the hydrogen peroxide to the hydrogenation step to circulate the working solution;
a working solution regeneration step of removing inactive substances generated as by-products accompanying the generation of hydrogen peroxide from the working solution to prepare a regenerated working solution; and
a process for preparing a recycling regenerated working solution, wherein the crude regenerated working solution is washed by water or alkali to prepare the recycling regenerated working solution,
the working solution regeneration step includes:
i) A first distillation step of recovering aromatic hydrocarbons by distillation performed at atmospheric pressure or below; and
ii) a second distillation step of recovering anthraquinones and trioctyl phosphate by distillation at a lower pressure and 160 ℃ or higher.
This embodiment is the same except that the method for producing hydrogen peroxide according to the present invention does not require alkali washing of the crude regeneration working solution, but washing with water may be used instead. As shown in example 4, even when the crude regeneration working solution is washed with only water, the hydrogenation activity of the regeneration working solution containing trioctyl phosphate can be improved as compared with the working solution in circulation. The above description of the hydrogen peroxide production method of the present invention is also applicable to the hydrogen peroxide production method a of the present invention, provided that alkali cleaning is not necessary.
Another aspect of the present invention relates to a method for producing a regenerative working solution for circulation (hereinafter, sometimes referred to as "method for producing a regenerative working solution for circulation a" according to the present invention), comprising:
a working solution regeneration step of removing an inactive substance from a working solution for hydrogen peroxide production containing an aromatic hydrocarbon, trioctyl phosphate, anthraquinones, and the inactive substance produced as a by-product with the production of hydrogen peroxide, to prepare a crude regeneration working solution from which the inactive substance has been removed; and
a process for preparing a recycling regenerated working solution, wherein the crude regenerated working solution is washed by water or alkali to prepare the recycling regenerated working solution,
the working solution regeneration step includes:
i) A first distillation step of recovering aromatic hydrocarbons by distillation performed at atmospheric pressure or below; and
ii) a second distillation step of recovering anthraquinones and trioctyl phosphate by distillation at a lower pressure and 160 ℃ or higher.
The characteristics of each step of the method for producing a recycled regenerated working solution a of the present invention are the same as those of each step corresponding to the method for producing hydrogen peroxide of the present invention.
Another aspect of the present invention relates to a method for producing hydrogen peroxide (hereinafter, sometimes referred to as "method for producing hydrogen peroxide B" according to the present invention), comprising:
a hydrogen peroxide production step of hydrogenating and oxidizing a working solution containing an aromatic hydrocarbon, a polar solvent and anthraquinones to produce hydrogen peroxide, extracting the hydrogen peroxide from the working solution, and returning the working solution after extracting the hydrogen peroxide to the hydrogenation step to circulate the working solution;
a working solution regeneration step of removing inactive substances generated as by-products accompanying the generation of hydrogen peroxide from the working solution to prepare a regenerated working solution; and
a process for preparing a recycling regenerated working solution, wherein the crude regenerated working solution is subjected to alkali cleaning to prepare the recycling regenerated working solution,
the working solution regeneration step includes:
i) A first distillation step of recovering aromatic hydrocarbons by distillation performed at atmospheric pressure or below; and
ii) a second distillation step of recovering anthraquinones by distillation at 160 ℃ or higher under a lower pressure,
the polar solvent is recovered in the first distillation step or the second distillation step.
This embodiment is the same as the hydrogen peroxide production method of the present invention except that the polar solvent contained in the working solution is not specifically trioctyl phosphate, and the polar solvent is recovered in the first distillation step or the second distillation step. As shown in example 4, the alkali washing of the crude regeneration working solution can improve the hydrogenation activity of the obtained regeneration working solution as compared with the washing with water, and it is considered that this is also the case in the working solution containing a polar solvent other than trioctyl phosphate. The above description of the hydrogen peroxide production method of the present invention is also applicable to the hydrogen peroxide production method B of the present invention, provided that the polar solvent is not specifically trioctyl phosphate, and the polar solvent is recovered in any one of the first distillation step and the second distillation step.
The polar solvent in the hydrogen peroxide production method B of the present invention is not particularly limited as long as it can dissolve the anthracenediphenols, and includes, for example, alcohols (e.g., diisobutylcarbinol (DIBC), 2-octanol), tetra-substituted ureas (e.g., tetrabutylurea (TBU)), phosphoric esters (e.g., trioctyl phosphate), 2-pyrrolidone, or alkyl cyclohexyl acetate (e.g., methylcyclohexyl acetate (MCHA)), and the like. The distillation step for recovering the polar solvent may be appropriately determined depending on the type of the polar solvent. For example, DIBC or 2-octanol may be recovered in the first distillation process, and TOP or TBU may be recovered in the second distillation process.
Another aspect of the present invention relates to a method for producing a regenerative working solution for circulation (hereinafter, sometimes referred to as "method for producing a regenerative working solution for circulation B" according to the present invention), comprising:
a working solution regeneration step of removing an inactive substance from a working solution for hydrogen peroxide production containing an aromatic hydrocarbon, a polar solvent, anthraquinones, and the inactive substance produced as a by-product in association with the production of hydrogen peroxide, to prepare a crude regenerated working solution from which the inactive substance has been removed; and
a process for preparing a recycling regenerated working solution, wherein the crude regenerated working solution is subjected to alkali cleaning to prepare the recycling regenerated working solution,
the working solution regeneration step includes:
i) A first distillation step of recovering aromatic hydrocarbons by distillation performed at atmospheric pressure or below; and
ii) a second distillation step of recovering anthraquinones by distillation at 160 ℃ or higher under a lower pressure,
the polar solvent is recovered in the first distillation step or the second distillation step.
The characteristics of each step of the recycling regeneration working solution producing method B of the present invention are the same as those of each step corresponding to the hydrogen peroxide producing method B of the present invention.
Another aspect of the present invention relates to a hydrogen peroxide production system (hereinafter sometimes referred to as "the hydrogen peroxide production system of the present invention") having a distillation column, a production tank, a cleaning tank, a hydrogenation column, an oxidation column, and an extraction column. The hydrogen peroxide production system of the present invention may have a front-stage distillation distillate tank and/or a rear-stage distillation distillate tank in addition to the above. One embodiment of the hydrogen peroxide production system according to the present invention will be described below with reference to the drawings.
Fig. 1 shows a hydrogen peroxide production system a of the present invention having a distillation column 1, a production tank 2, a cleaning tank 3, a hydrogenation column 4, an oxidation column 5, an extraction column 6, a front-stage distillation distillate tank 9 and a rear-stage distillation distillate tank 10. Distillation column 1 has an unknown component discharge line 8 and a distillate transfer line 7, distillate transfer line 7 and front-stage distillation distillate tank 9 are connected by front-stage distillation distillate transfer line 7a, distillate transfer line 7 and rear-stage distillation distillate tank 10 are connected by rear-stage distillation distillate transfer line 7b, front-stage distillation distillate tank 9 and preparation tank 2 are connected by front-stage distillation distillate supply line 11, rear-stage distillation distillate tank 10 and preparation tank 2 are connected by rear-stage distillation distillate supply line 12, preparation tank 2 and cleaning tank 3 are connected by crude regeneration working solution supply line 13, cleaning tank 3 is connected with alkali solution supply line 14 and water supply line 15, cleaning tank 3 has waste liquid line 17, cleaning tank 3 and hydrogenation column 4 are connected by recycle regeneration working solution supply line 16, hydrogenation column 4 has hydrogenation agent supply line 19 and hydrogenation agent circulation line 18, hydrogenation column 4 and oxidation column 5 are connected by hydrogenation working solution supply line 20, oxidation column 5 has oxidation agent supply line 21 and exhaust line 22, oxidation column 5 and extraction column 6 are connected by oxidation working solution supply 23, extraction solution recovery tank 3 is connected by extraction working solution supply line 25 and hydrogen peroxide solution supply line 26, and hydrogen peroxide solution supply line 25 is connected by post-distillation working solution supply line 26. The front-stage distilled distillate transfer line 7a, the rear-stage distilled distillate transfer line 7b, the unidentified substance discharge line 8, the front-stage distilled distillate supply line 11, the rear-stage distilled distillate supply line 12, the crude regeneration working solution supply line 13, the alkali solution supply line 14, the water supply line 15, the recycle regeneration working solution supply line 16, and the waste liquid line 17 have valves V. The distillation column 1 can realize reduced pressure distillation (e.g., 0.1kPa to 15 kPa) at various temperatures (e.g., 120 ℃ C. To 260 ℃ C.).
The working solution is reacted with a hydrogen-containing hydrogenating agent 32 (for example, hydrogen gas, a mixture of an inert gas (nitrogen gas, etc.) and hydrogen gas, etc.) from a hydrogenating agent supply line 19 in a hydrogenating tower 4 to produce anthracenediphenols from anthraquinones. The unreacted hydrogenating agent is repeatedly supplied to the hydrogenation column 4 via the hydrogenating agent circulation line 18. The hydrogenated working solution is fed to the oxidation column 5 through the hydrogenation working solution supply line 20, and the anthracene-diphenols are oxidized by an oxygen-containing oxidizing agent 33 (for example, air, oxygen, etc.) fed from the oxidizing agent supply line 21 to produce anthraquinones and hydrogen peroxide. Unreacted oxidant 34 is discharged from the exhaust line 22. The oxidized working solution containing hydrogen peroxide enters the extraction column 6 through the oxidation working solution supply line 23, and the generated hydrogen peroxide is recovered from the hydrogen peroxide transfer line 25 by forming hydrogen peroxide water 36 from the water 35 supplied from the water supply line 24. A part of the hydrogen peroxide-extracted working solution enters the distillation column 1 through the hydrogen peroxide-extracted working solution supply line 26, and the remaining hydrogen peroxide-extracted working solution circulation line 27 merges with the circulating regenerated working solution supply line 16 and returns to the hydrogenation column 4.
The working solution after hydrogen peroxide extraction, which has entered the distillation column 1, is supplied to a front-stage distillation performed at atmospheric pressure or below. The aromatic hydrocarbon-containing fore-stage distillate distilled by the fore-stage distillation is stored in a fore-stage distillate tank 9 through a distillate transfer line 7 and a fore-stage distillate transfer line 7 a. The residue remaining in the distillation column 1 is supplied to the latter distillation stage carried out at 160 ℃ or higher at a lower pressure than the former distillation stage. The post-distillation distillate containing anthraquinones and trioctyl phosphate distilled by the post-distillation is stored in a post-distillation distillate tank 10 through a distillate transfer line 7 and a post-distillation distillate transfer line 7 b. The unidentified component 28 as a residue after the subsequent distillation is discharged from the unidentified component discharge line 8. The front-stage distillate stored in the front-stage distillate tank 9 and the rear-stage distillate stored in the rear-stage distillate tank 10 are fed into the production tank 2 through the front-stage distillate supply line 11 and the rear-stage distillate supply line 12, respectively, and mixed to produce a crude regeneration working solution. The produced crude regeneration working solution enters the cleaning tank 3 through the crude regeneration working solution supply line 13. The crude regeneration working solution is washed with the alkaline solution 29 supplied from the alkaline solution supply line 14, and then, if necessary, with the water 30 supplied from the water supply line 15, to obtain a regeneration working solution for circulation. The alkali solution or water used for washing is discharged from the waste liquid line 17 as waste liquid 31. The circulating regeneration working solution is supplied through the circulating regeneration working solution supply line 16, and is merged with the working solution from the circulating line 27 of the working solution after hydrogen peroxide extraction in the middle, and enters the hydrogenation column 4.
The hydrogen peroxide production system of the present invention may further have a recrystallization tank. An outline of the hydrogen peroxide production system B of the present invention having a recrystallization tank will be described with reference to fig. 2. In the hydrogen peroxide production system B, the same components as those of the hydrogen peroxide production system a shown in fig. 1 are denoted by the same reference numerals, and the description thereof will be omitted.
In this embodiment, the post-distillation distillate supply line 12 connected to the post-distillation distillate tank 10 is connected to the recrystallization vessel 37, and the anthraquinone supply line 40 connected to the recrystallization vessel 37 is connected to the production vessel 2. The recrystallization tank 37 is further connected to a recrystallization solvent supply line 39, a waste liquid line 41, and a filtrate transfer line 42, the recrystallization solvent supply line 39 connecting the recrystallization solvent tank 38 to the recrystallization tank 37, and the filtrate transfer line 42 connecting the recrystallization tank 37 to the distillation column 1. The recrystallization solvent pot 38 communicates with the distillate transfer line 7 through a distillate recrystallization solvent transfer line 7d, and the production tank 2 communicates with the distillate transfer line 7 through a distillate TOP transfer line 7 c. The recrystallization tank 37 is provided with a temperature control device, and can realize heating dissolution of anthraquinones in a recrystallization solvent and subsequent recrystallization of anthraquinones by cooling. The recrystallization tank 37 further has a filter for filtering and separating the recrystallized anthraquinones.
In this embodiment, the post-distillation distillate stored in the post-distillation distillate tank 10 is introduced into the recrystallization vessel 37 through the post-distillation distillate supply line 12. The recrystallization solvent is supplied from the recrystallization solvent supply line 39 to the recrystallization tank 37, and the anthraquinones contained in the distillate are recrystallized by cooling after heating and dissolving the anthraquinones. The recrystallized anthraquinones are recovered by a filter provided in the recrystallization tank 37, and sent to the production tank 2 through an anthraquinone feed line 40. The filtrate containing trioctyl phosphate and the recrystallization solvent, which has passed through the filter, is sent to the distillation column 1 through a filtrate transfer line 42, or is discarded through a waste liquid line 41. The recrystallization solvent and trioctyl phosphate are distilled off from the filtrate fed to the distillation column 1 by distillation, respectively, and the distilled recrystallization solvent is stored in the recrystallization solvent tank 38 through the distillate transfer line 7 and the distilled recrystallization solvent transfer line 7d, and the distilled trioctyl phosphate is fed to the production tank 2 through the distillate transfer line 7 and the distilled TOP transfer line 7 c.
The hydrogen peroxide production system of the present invention is not particularly limited to the above-described embodiment, and various modifications can be made within the scope of the gist of the present invention. For example, in the hydrogen peroxide production system a shown in fig. 1, the following modes are possible: (A1) A front-stage distillation distillate tank 9 and a front-stage distillation distillate transfer line 7a connected thereto are not provided, and the front-stage distillation distillate supply line 11 is used to communicate the distillate transfer line 7 with the production tank 2; (A2) A post-distillation distillate tank 10 and a post-distillation distillate transfer line 7b connected thereto are not provided, and the distillate transfer line 7 and the production tank 2 are communicated with each other by a post-distillation distillate supply line 12; (A3) The front-stage distillation distillate tank 9 and the front-stage distillation distillate transfer line 7a connected thereto, and the rear-stage distillation distillate tank 10 and the rear-stage distillation distillate transfer line 7b connected thereto are not provided, and the front-stage distillation distillate supply line 11 and the rear-stage distillation distillate supply line 12 are used to communicate the distillate transfer line 7 with the production tank 2; (A4) The distillation column 1 and the production tank 2 are connected by the front-stage distillation distillate supply line 11 and the rear-stage distillation distillate supply line 12 without providing the distillate transfer line 7, the front-stage distillation distillate tank 9 and the front-stage distillation distillate transfer line 7a connected thereto, and the rear-stage distillation distillate tank 10 and the rear-stage distillation distillate transfer line 7b connected thereto.
In addition to the above-described modifications (A1) to (A4) of the hydrogen peroxide production system a, the hydrogen peroxide production system B shown in fig. 2 may be, for example, the following: (B1) The filtrate transfer line 42 and the distillate recrystallization solvent transfer line 7d are not provided; (B2) A distillate TOP tank is arranged, the distillate conveying pipeline 7 is communicated with the distillate TOP tank by a distillate TOP conveying pipeline 7c, and the distillate TOP tank is communicated with the preparation tank 2 by a distillate TOP supply pipeline; (B3) Instead of providing a filter in the recrystallization tank 37, the filter is provided in the middle of the anthraquinone-based supply line 40.
In either of the hydrogen peroxide production systems a and B, a pump, an additional valve, a manifold line, or a valve removed from a line having a valve may be provided in at least 1 line, as necessary.
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[ example ]
< analytical method >)
The aromatic hydrocarbons, trioctyl phosphate, 2-ethylanthraquinone and 2-ethylanthraquinone in the working solution and the samples obtained in each operation were quantified using a gas chromatography apparatus. The gas chromatograph apparatus used was a gas chromatograph GC-2014 manufactured by shimadzu corporation. The column used was a capillary column DB-5MS manufactured by Agilent corporation. All the substances other than the above-mentioned components are referred to as "unknown components". It is presumed that most of the "unknown ingredient" is an inactive substance.
The densities of the initial working solution and the recycled regenerated working solution were measured using a densitometer DA-640 manufactured by Kyoto electronic industries, and the viscosities were measured using a type B viscometer manufactured by Tokyo instruments.
The hydrogenation activity of the initial working solution and the recycled regeneration working solution was evaluated in the following manner. A100 mL 2-neck flask was charged with a hydrogenation catalyst and a working solution. The stirrer was connected to one of the 1 ports of the flask, and the other 1 port was connected to a hydrogen supply unit. And the flask was sealed. The hydrogen supply unit includes a hydrogen gauge tube, a U-tube pressure gauge, and a water reservoir, and is capable of maintaining the internal pressure of the flask equal to the atmospheric pressure by adjusting the height of the water reservoir in accordance with the change in the liquid level of the U-tube pressure gauge during the hydrogenation reaction. The hydrogen absorption amount was measured as the difference in the liquid level in the hydrogen measuring tube. The flask was immersed in a water bath at 30℃and allowed to stand for 10 minutes. After the evacuation and the introduction of hydrogen gas into the flask were repeated 3 times, the stirrer was operated. The amount of hydrogen absorbed was measured from the start of hydrogen absorption to 30 minutes later. The hydrogen absorption amount was converted to a value at 0℃and 1 atm. The activity value of the hydrogenation catalyst was expressed as a standard state hydrogen absorption rate per unit weight of the hydrogenation catalyst [ NmL/(min×g) ]. The hydrogenation catalyst used was 2 wt% Pd/silica 0.05g after drying at 120℃or 1 wt% Pd/silica alumina 0.1g after drying at 120 ℃.
Example 1
The first distillation step and the second distillation step of the present invention are performed on a small scale, and the initial working solution and the recycled regeneration working solution are compared.
< first distillation procedure >
400g of the working solution was charged into a 500mL flask equipped with a distillation apparatus. Distillation was carried out under reduced pressure, and the vacuum was always controlled at 1.3kPa. The temperature in the flask was raised from room temperature to 182 ℃. Distillation was continued until the distillate was no longer distilled off at a final temperature of 1.3kPa and 182 ℃.
< second distillation procedure >
The residue obtained in the first distillation step is distilled at a lower pressure than the first distillation step. The vacuum level was varied from 0.03kPa to 0.15kPa during a period of time from the start of distillation, and finally stabilized at 0.08kPa. The temperature in the flask was raised from room temperature to 202 ℃. Distillation was continued until the distillate was no longer distilled out at 0.08kPa, 202 c.
< distillation results >
The compositions of the initial working solution, the distillate recovered by each distillation step, and the residue are shown in table 1. As aromatic hydrocarbons, high boiling aromatic naphtha (Swasol 1500, produced by Wan Petroleum chemical Co., ltd., CAS No. 64142-94-5) was used (the same applies to examples 2 to 4). Among them, in distillation, various reactions occur as represented by conversion of tetrahydroanthraquinone to anthraquinone, and therefore, depending on the components, the weight may be increased as compared with the initial working solution. In addition, the "loss amount" means an amount of loss in an experiment (the reason may be considered to be due to loss in a cold trap or a pump, or the like).
[ Table 1 ]
TABLE 1 composition of initial working solution and distillate and residue (Material balance)
< evaluation of regenerated working solution for circulation >
A regenerated working solution is prepared from the distillate recovered in each distillation step. The fraction of the first distillation step is added to the fraction of the second distillation step to obtain a solvent composition ratio close to that of the initial working solution, thereby producing a crude regenerated working solution. The compositions of the initial working solution and the crude regeneration working solution are shown below.
[ Table 2 ]
TABLE 2 composition of initial working solution and crude regeneration working solution
The crude regeneration working solution was washed with a 2-fold volume of a 30wt% aqueous sodium hydroxide solution and a 2-fold volume of pure water in this order to obtain a regeneration working solution for recycling. The results of comparing the densities, viscosities, and hydrogenation activities of the initial working solution and the recycle regeneration working solution are shown below. Wherein, when evaluating hydrogenation activity, 0.05g of 2 wt% Pd/silica dried at 120℃was used as a hydrogenation catalyst.
[ Table 3 ]
TABLE 3 comparison of initial working solution with circulating regeneration working solution
< isolation of anthraquinones >
To 32g of the distillate from the second distillation step, about 200mL of ethanol was added, and the mixture was heated to dissolve the ethanol and then cooled to room temperature (recrystallization). The crystals were separated by filtration and dried. The composition of the distillate from the second distillation step and the crystals recovered by recrystallization are shown below. Anthraquinones can be separated from trioctyl phosphate and unidentified components at a recovery rate of 64%. By this method, the recovered anthraquinones can be reused as components of the working solution.
[ Table 4 ]
TABLE 4 composition of distillate from the second distillation step and crystals recovered by recrystallization
Example 2
The first distillation step and the second distillation step of the present invention were carried out under different conditions from those of example 1, and the initial working solution and the regeneration working solution for circulation were compared.
< first distillation Process >
351g of the working solution was charged into a 500mL flask equipped with a distillation apparatus. Distillation was carried out under reduced pressure, and the vacuum was always controlled at 1.3kPa. The temperature in the flask was raised from room temperature to 157 ℃. Distillation was continued until the distillate was no longer distilled off at 1.3kPa, 157 c.
< second distillation Process >
The residue obtained in the first distillation step is distilled at a lower pressure than the first distillation step. The vacuum degree varies from 10Pa to 150Pa over a period of time from the start of distillation, and finally stabilizes at 0.01kPa to 0.04kPa. The temperature in the flask was raised from room temperature to 181 ℃. Distillation was continued until the distillate was no longer distilled off at 0.01kPa at 181 c.
< distillation results >
The compositions of the initial working solution, the distillate recovered by each distillation step, and the residue are shown in table 5.
[ Table 5 ]
TABLE 5 composition of initial working solution and distillate and residue (Material balance)
A crude regeneration working solution was prepared in the same manner as in example 1. Table 6 shows the compositions of the initial working solution and the crude regeneration working solution.
[ Table 6 ]
TABLE 6 composition of initial working solution and crude regeneration working solution
A regeneration working solution for circulation was prepared by the same washing procedure as in example 1. Table 7 shows the density, viscosity, and hydrogenation activity of the initial working solution and the recycle regeneration working solution. Wherein, when evaluating hydrogenation activity, 0.1g of 1 wt% Pd/silica alumina dried at 120℃was used as a hydrogenation catalyst.
[ Table 7 ]
TABLE 7 comparison of initial working solution with circulating regeneration working solution
Example 3
The first distillation step and the second distillation step of the present invention were carried out under different conditions from those of examples 1 and 2, and the initial working solution and the recycled regeneration working solution were compared.
< first distillation Process >
351g of the same working solution as in example 2 was charged into a 500mL flask equipped with a distillation apparatus. Distillation was carried out under reduced pressure, and the vacuum was always controlled at 1.3kPa. The temperature in the flask was raised from room temperature to 180 ℃. Distillation was continued until the distillate was no longer distilled out at 1.3kPa at 180 ℃.
< second distillation Process >
The residue obtained in the first distillation step is distilled at a lower pressure than the first distillation step. The vacuum was always controlled at 0.13kPa. The temperature in the flask was raised from room temperature to 250 ℃. Distillation was continued until the distillate was no longer distilled off at 0.13kPa, 250 c.
< distillation results >
The compositions of the initial working solution, the distillate recovered by each distillation step, and the residue are shown in table 8.
[ Table 8 ]
TABLE 8 composition of initial working solution and distillate and residue (Material balance)
A crude regeneration working solution was prepared in the same manner as in example 1. Table 9 shows the compositions of the initial working solution and the crude regeneration working solution.
[ Table 9 ]
TABLE 9 composition of initial working solution and crude regeneration working solution
A regeneration working solution for circulation was prepared by the same washing procedure as in example 1. Table 10 shows the comparison of density, viscosity and hydrogenation activity. Wherein, when evaluating hydrogenation activity, 0.1g of 1 wt% Pd/silica alumina dried at 120℃was used as a hydrogenation catalyst.
[ Table 10 ]
TABLE 10 evaluation of initial working solution and regenerated working solution for circulation
Example 4
The crude regeneration working solution prepared in example 2 was washed 2 times with 2-fold volume of pure water to obtain a regeneration working solution for recycling (pure water washing). The hydrogenation activity test was carried out in the same manner as in example 2. The hydrogenation catalyst used was 1 wt% Pd/silica alumina 0.1g dried at 120 ℃. Table 11 shows the results of the hydrogenation activity test. The regenerated working solution for circulation which was subjected to only pure water washing had higher hydrogenation activity than the initial working solution, but the regenerated working solution for circulation which was subjected to alkali washing (example 2) had higher hydrogenation activity.
[ Table 11 ]
TABLE 11 hydrogenation Activity
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Claims (16)
1. A method for producing hydrogen peroxide, comprising:
a hydrogen peroxide production step of hydrogenating and oxidizing a working solution containing an aromatic hydrocarbon, trioctyl phosphate and anthraquinones to produce hydrogen peroxide, extracting the hydrogen peroxide from the working solution, and returning the working solution after extracting the hydrogen peroxide to the hydrogenation step to circulate the working solution;
a working solution regeneration step of removing an inactive substance generated as a by-product accompanying the generation of hydrogen peroxide from the working solution to prepare a crude regenerated working solution from which the inactive substance has been removed; and
a process for producing a recycled regenerated working solution, wherein the crude regenerated working solution is subjected to alkali cleaning to produce a recycled regenerated working solution,
the working solution regeneration process includes:
i) A first distillation step for recovering aromatic hydrocarbons by distillation at 140-190 ℃ under atmospheric pressure or below; and
ii) a second distillation step of recovering anthraquinones and trioctyl phosphate by distillation at a lower pressure and 160 ℃ or higher.
2. The method for producing hydrogen peroxide according to claim 1, wherein:
The pressure in the first distillation step is in the range of 1kPa to 100 kPa.
3. The method for producing hydrogen peroxide according to claim 1 or 2, wherein:
the pressure in the second distillation step is 1kPa or less.
4. A method for producing hydrogen peroxide according to any one of claims 1 to 3, wherein:
the temperature in the second distillation step is in the range of 160 ℃ to 300 ℃.
5. The method for producing hydrogen peroxide according to any one of claims 1 to 4, wherein:
the anthraquinones include alkylanthraquinone and alkyltetrahydroanthraquinone.
6. The method for producing hydrogen peroxide according to any one of claims 1 to 5, wherein:
comprises a step of returning the recycling regeneration working solution to the hydrogen peroxide production step.
7. The method for producing hydrogen peroxide according to claim 6, wherein:
the solvent composition ratio of the crude regeneration working solution is within a range of + -20% relative to the solvent composition ratio of the working solution circulated in the hydrogen peroxide production process.
8. The method for producing hydrogen peroxide according to claim 6 or 7, wherein:
the concentration of the anthraquinones in the crude regeneration working solution is in a range of not less than the concentration of the anthraquinones in the working solution circulated in the hydrogen peroxide production process and not more than the saturation concentration of the anthraquinones.
9. The method for producing hydrogen peroxide according to any one of claims 6 to 8, wherein:
in the above-described regeneration working solution preparation step for circulation, the regeneration working solution is adjusted to 20% to 160% of the saturated water content.
10. The method for producing hydrogen peroxide according to any one of claims 6 to 9, wherein:
the process for preparing the recycling regenerated working solution further comprises a process of washing the regenerated working solution after alkali cleaning.
11. The method for producing hydrogen peroxide according to any one of claims 1 to 10, wherein:
further comprising a step of separating anthraquinone and trioctyl phosphate from the distillate of the second distillation step.
12. The method for producing hydrogen peroxide according to claim 11, wherein:
the step of separating anthraquinone and trioctyl phosphate is performed by recrystallization.
13. A hydrogen peroxide manufacturing system having a distillation column, a preparation tank, a cleaning tank, a hydrogenation column, an oxidation column, and an extraction column, the hydrogen peroxide manufacturing system characterized by:
the distillation column has an unknown component discharge line, the distillation column and the preparation tank are communicated by a front-stage distillation distillate supply line and a rear-stage distillation distillate supply line, the preparation tank and the cleaning tank are communicated by a crude regeneration working solution supply line, the cleaning tank is connected with an alkali solution supply line and a water supply line, the cleaning tank has a waste liquid line, the cleaning tank and the hydrogenation column are communicated by a recycle regeneration working solution supply line, the hydrogenation column is connected with a hydrogenating agent supply line, the hydrogenation column and the oxidation column are communicated by a hydrogenation working solution supply line, the oxidation column is connected with an oxidizing agent supply line, the oxidation column and the extraction column are communicated by an oxidation working solution supply line, the extraction column has a hydrogen peroxide transfer line, the distillation column and the extraction column are communicated by a supply line of working solution after hydrogen peroxide extraction, the distillation column is configured to perform front-stage distillation for recovering aromatic hydrocarbons by distillation at an atmospheric pressure or lower and a temperature of 140 ℃ to 190 ℃, and then rear-stage distillation recovering anthraquinones and trioctyl phosphate by distillation at a lower pressure and a temperature of 160 ℃ or higher.
14. The system of claim 13, wherein:
the distillation tower is communicated with the front-stage distillation distillate tank through a front-stage distillation distillate conveying pipeline, and the front-stage distillation distillate tank is communicated with the preparation tank through a front-stage distillation distillate supply pipeline.
15. The system of claim 13, wherein:
the distillation tower is communicated with the back-end distillation distillate tank through a back-end distillation distillate conveying pipeline, and the back-end distillation distillate tank is communicated with the preparation tank through a back-end distillation distillate supply pipeline.
16. The system of claim 13, wherein:
the device is characterized by further comprising a recrystallization tank, wherein the recrystallization tank is provided with a filter and a waste liquid pipeline, the recrystallization tank is connected with a recrystallization solvent supply pipeline, the recrystallization tank is communicated with the distillation tower through a rear-stage distillation distillate supply pipeline, and the recrystallization tank is communicated with the preparation tank through an anthraquinone supply pipeline.
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| JP2017173394A JP6972802B2 (en) | 2017-09-08 | 2017-09-08 | Method for producing hydrogen peroxide |
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| CN201811036580.4A CN109467056A (en) | 2017-09-08 | 2018-09-06 | Peroxidating method for preparing hydrogen |
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| 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 |
| CN113371744A (en) * | 2021-06-04 | 2021-09-10 | 刘�文 | Waste activated alumina treatment process |
| 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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| CN101891158A (en) * | 2010-07-15 | 2010-11-24 | 江山市双氧水有限公司 | Treatment method for continuous regeneration of hydrogen peroxide working solution produced by anthraquinone process |
| JP2014224009A (en) * | 2013-05-16 | 2014-12-04 | 三菱瓦斯化学株式会社 | Actuating solution used for hydrogen peroxide production, processing method of the same, and method of hydrogen peroxide production using the same |
| US10138123B2 (en) * | 2013-08-23 | 2018-11-27 | Mitsubishi Gas Chemical Company, Inc. | Method for regenerating working solution used for production of hydrogen peroxide and method for producing hydrogen peroxide using regenerated working solution |
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| JP6972802B2 (en) | 2021-11-24 |
| JP2019048740A (en) | 2019-03-28 |
| CN208964546U (en) | 2019-06-11 |
| TW201912567A (en) | 2019-04-01 |
| CN109467056A (en) | 2019-03-15 |
| KR102617500B1 (en) | 2023-12-22 |
| TWI770262B (en) | 2022-07-11 |
| KR20190028289A (en) | 2019-03-18 |
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