CN113697888A - Extracting agent and method for treating phenol-ammonia wastewater - Google Patents
Extracting agent and method for treating phenol-ammonia wastewater Download PDFInfo
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- CN113697888A CN113697888A CN202111021158.3A CN202111021158A CN113697888A CN 113697888 A CN113697888 A CN 113697888A CN 202111021158 A CN202111021158 A CN 202111021158A CN 113697888 A CN113697888 A CN 113697888A
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- Prior art keywords
- phenol
- extractant
- ammonia
- extraction
- agent
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- 239000002351 wastewater Substances 0.000 title claims abstract description 84
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 157
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 70
- 230000002195 synergetic effect Effects 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 230000007935 neutral effect Effects 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011574 phosphorus Substances 0.000 claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000002378 acidificating effect Effects 0.000 claims abstract description 23
- 239000012074 organic phase Substances 0.000 claims abstract description 23
- XABJJJZIQNZSIM-UHFFFAOYSA-N azane;phenol Chemical compound [NH4+].[O-]C1=CC=CC=C1 XABJJJZIQNZSIM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 239000002671 adjuvant Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000012071 phase Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000012047 saturated solution Substances 0.000 claims abstract description 3
- 150000002989 phenols Chemical class 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 33
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 14
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- -1 phosphoric acid triesters Chemical class 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000009615 deamination Effects 0.000 claims description 5
- 238000006481 deamination reaction Methods 0.000 claims description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 3
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 claims description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229930016911 cinnamic acid Natural products 0.000 claims description 3
- 235000013985 cinnamic acid Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 235000012254 magnesium hydroxide Nutrition 0.000 claims description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 94
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000008442 polyphenolic compounds Chemical class 0.000 description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 235000013824 polyphenols Nutrition 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 108010037444 diisopropylglutathione ester Proteins 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 2
- 229960001553 phloroglucinol Drugs 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- WBLGXIFKKXGJGJ-UHFFFAOYSA-N CC(CCCCCC)(C)OP(O)(=O)C Chemical compound CC(CCCCCC)(C)OP(O)(=O)C WBLGXIFKKXGJGJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention relates to an extracting agent for treating phenol-ammonia wastewater, a method and a process, which relate to the technical field of sewage treatment and comprise the following components (by volume percent): 0.1 to 3 percent of alkaline amine extractant, 0.1 to 5 percent of neutral phosphorus-containing extractant and 92 to 99.79 percent of main extractant; which comprises the following steps: step 1: uniformly mixing an alkaline amine extractant, a neutral phosphorus-containing extractant, an acidic adjuvant and a main extractant to obtain an organic phase, and mixing the organic phase with a pre-saturated solution acidic adjuvant to obtain a synergistic extractant A; step 2: adding a phenol-ammonia wastewater mixture B to be separated and a main extracting agent F into a first extraction tower for separation to form a phenol-ammonia extraction phase G and a phenol-ammonia solution C; and step 3: extracting the synergistic extraction agent A obtained in the step 1 and the phenol ammonia solution C in a second extraction tower to obtain an organic phase D of phenol ammonia and dephenolized wastewater H; and 4, step 4: separating the organic phase D of the phenol ammonia in a rectifying tower to obtain a main extracting agent F and a mixture E at the bottom of the rectifying tower; and 5: and (4) mixing the mixture E obtained in the step (4) with a stripping agent I in a stripping kettle to generate a sodium phenolate aqueous solution M and a synergistic extraction agent. The method has the advantages of low cost, high extraction rate and simple operation method, and effectively reduces harmful substances in the sewage.
Description
Technical Field
The invention relates to an extracting agent and a method for treating phenol-ammonia wastewater, belonging to the technical field of sewage treatment.
Background
In the coal chemical industry, phenol-ammonia wastewater is one of the wastewater which is difficult to treat, the wastewater contains more phenol types, organic compounds such as alcohols, ketones, pyridine, anthracene and the like and derivatives thereof, and the rest components comprise hydrogen sulfide, carbon dioxide, hydrocyanic acid, coal powder, inorganic salt, tar and colloid high molecular compounds.
The process commonly adopted at present comprises several main processes of deacidification and deamination, extraction and deoiling, extraction and dephenolization and a combined strengthening means, wherein the process route of azeotropic distillation regeneration and water azeotropic recovery of the extracting agent is adopted for extracting agent recovery, the extracting agent mainly comprises one of diisopropyl ether, methyl isobutyl ketone, xylene and the like, the phenol content of the treated wastewater is still 800-1100mg/L, the polyphenol is mainly used, and a part of soluble nitrogenous organic matters exist, so that the toxicity to bacteria in the biochemical treatment process is high, a large amount of bacteria can be frequently killed, and the treatment of the wastewater becomes a main bottleneck restricting the development of the industry.
Chinese patent CN201611191625.6 proposes a combined extracting agent, which adopts n-propyl propionate and anisole as extracting agents, and the main disadvantages of the formula are that n-propyl propionate is easy to be hydrolyzed into lactic acid and n-propanol after being recycled in acid-base and heating environments for a long time, the hydrolysis product has strong water solubility, and forms a new COD contribution component; anisole also has a tendency to hydrolyze in alkaline and heated environments, thus presenting difficulties and potential technical risks for large-scale industrial applications.
Disclosure of Invention
Aiming at the problems, the invention provides an extracting agent and a method for treating phenol-ammonia wastewater, which can effectively separate unit phenol and polyhydric phenol, have low cost and high extraction rate, and the technical scheme is as follows:
an extracting agent for treating phenol-ammonia wastewater comprises the following components (by volume percent): 0.1 to 3 percent of alkaline amine extractant, 0.1 to 5 percent of neutral phosphorus-containing extractant and 92 to 99.79 percent of main extractant.
As a preferred scheme, the main extracting agent is selected from at least one of ethyl acetate, butanol, heptane, octane, methyl isobutyl ketone and diisopropyl ether;
the alkaline amine extractant is selected from at least one of dodecylamine, hexadecylamine, piperazine, octadecylamine, N-ethylpiperazine and methylpiperazine.
The acidic adjuvant is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, thiocyanic acid, perchloric acid, cinnamic acid, naphthenic acid, acetic acid, glutamic acid, tartaric acid, citric acid, glycolic acid and ethylenediamine tetraacetic acid;
as a preferred scheme, the neutral phosphorus-containing extractant has the structure
Wherein K2, K3 and K4 are independently selected from any one of a linear or branched alkyl group having 2 to 8 carbon atoms, a linear or branched alkoxy group having 4 to 8 carbon atoms, wherein at least two of K2, K3 and K4 are the same.
In a preferred embodiment, the neutral phosphorus-containing extractant is at least one selected from the group consisting of a phosphoric acid triester, a monoalkyl phosphoric acid diester, a dialkyl phosphoric acid monoester, and a trialkyl phosphorus oxide.
As a preferred scheme, the acid auxiliary agent is also included in 0.01-1% (by volume percentage). A method for treating phenol-ammonia wastewater, comprising the steps of:
step 1: uniformly mixing an alkaline amine extractant, a neutral phosphorus-containing extractant, an acidic adjuvant and a main extractant to obtain an organic phase, and mixing the organic phase with a pre-saturated solution acidic adjuvant to obtain a synergistic extractant A;
step 2: adding the phenol-ammonia wastewater mixture B to be separated and a main extracting agent F into a first extraction tower for separation to obtain a phenol-ammonia extraction phase G and a phenol-ammonia solution C;
and step 3: extracting the synergistic extraction agent A obtained in the step 1 and the phenol ammonia solution C obtained in the step 2 in a second extraction tower to obtain an organic phase D of phenol ammonia and dephenolized wastewater H;
and 4, step 4: separating the organic phase D of the phenol ammonia in a rectifying tower to obtain a main extracting agent F and a mixture E at the bottom of the rectifying tower;
and 5: and (4) mixing the mixture E obtained in the step (4) with a stripping agent I in a stripping kettle to generate a sodium phenolate aqueous solution M and a synergistic extraction agent.
In a preferable scheme, in the step 2, the volume ratio of the phenol-ammonia wastewater mixture B to be separated to the main extracting agent is as follows: 3: 1-7: 1;
in the step 3, the volume ratio of the synergistic extraction agent A to the phenol ammonia solution C is 50-90: 50-10;
in the step 5, the volume ratio of the mixture E to the stripping agent is 1: 1-1: 4.5.
As a preferable scheme, in the step 1, the reaction temperature of the organic phase and the acidic adjuvant is 40-55 ℃, and the extraction time is 10-15 min;
in the step 4, the pressure of the rectifying tower operation is 105-130 KPa.
Preferably, in the step 2, the phenol-ammonia wastewater mixture B to be separated is a solution containing both phenols and salt wastewater ions, and the concentration of phenols in the phenol-ammonia wastewater mixture B to be separated is 1000mg/L to 20000 mg/L;
in the step 5, the stripping agent is selected from an alkali solution, and the alkali in the alkali solution is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia water and magnesium hydroxide.
In a preferable scheme, in the step 2, the phenol-ammonia wastewater mixture B to be separated is subjected to a deamination process by reacting with alkali before entering the first extraction tower.
The invention has the beneficial effects that:
the method can effectively separate the unit phenol and the polyphenol, has low cost, high extraction rate and simple operation method, and effectively reduces harmful substances in the sewage.
Drawings
FIG. 1 is a process flow diagram of a process for treating phenol ammonia wastewater.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The synergistic extraction agent and the method for separating phenol-ammonia wastewater provided by the application are specifically described below.
The inventor obtains the following results through the research on the phenol ammonia wastewater solvent extraction separation system:
DIPE system: the organic phase extractant is diisopropyl ether, and the water phase is phenol ammonia water solution. The system preferentially extracts unit phenol in the water phase, and has more dependence on the acidic pH value of the extraction environment and more residual polyphenol.
MIBK extractant: the effect of methyl isobutyl ketone on treating the wastewater is better than that of diisopropyl ether, and depends on an acidic environment with a lower PH value, but the COD and the polyphenol content in the treated wastewater are still about 800mg/L, and the separation effect is poor.
N-propyl propionate and anisole extractant: the main extractant is recycled in a large amount, is easy to hydrolyze into lactic acid and propanol, and the synergistic extractant has higher price, does not azeotrope with water and is not easy to separate.
Therefore, the inventor creatively proposes a novel synergistic extractant for separating phenol ammonia wastewater, which comprises a small amount of basic amine extractant, a small amount of neutral phosphorus-containing extractant and a small amount of cheap main extractant.
The invention designs an extracting agent for treating phenol-ammonia wastewater, which comprises the following components in percentage by volume: 0.1 to 3 percent of alkaline amine extractant, 0.1 to 5 percent of neutral phosphorus-containing extractant, 0.01 to 1 percent of acidic auxiliary agent and 92 to 99.79 percent of main extractant. Preferably 0.5-1.5 percent of alkaline amine extractant, 0.2-2 percent of neutral phosphorus-containing extractant, 0.01-1 percent of acidic adjuvant and 96-99 percent of main extractant.
As a preferred technical scheme, the main extracting agent is selected from at least one of ethyl acetate, butanol, heptane, octane, methyl isobutyl ketone and diisopropyl ether;
the alkaline amine extractant is selected from at least one of dodecylamine, hexadecylamine, piperazine, octadecylamine, N-ethylpiperazine and methylpiperazine.
The acidic adjuvant is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, thiocyanic acid, perchloric acid, cinnamic acid, naphthenic acid, acetic acid, glutamic acid, tartaric acid, citric acid, glycolic acid and ethylenediamine tetraacetic acid;
the neutral phosphorus-containing extractant has the structure of
Wherein K2, K3 and K4 are independently selected from any one of a linear or branched alkyl group having 2 to 8 carbon atoms, a linear or branched alkoxy group having 4 to 8 carbon atoms, wherein at least two of K2, K3 and K4 are the same, preferably, K2, K3 and K4 are all the same. The neutral phosphorus-containing extractant is selected from at least one of phosphoric acid triester, monoalkyl phosphoric acid diester, dialkyl phosphoric acid monoester and trialkyl phosphine oxide. Preferably, the neutral phosphorus-containing extractant is selected from at least one of tributyl phosphate, trioctyl phosphate, dimethylheptyl methylphosphonate, octyl dioctylphosphonate, tributyl phosphine oxide and trioctyl phosphine oxide
Fig. 1 is a flow chart of treating phenol-ammonia wastewater, which includes a first extraction tower 1, a second extraction tower 2, a rectification tower 3, a back-extraction kettle 4, a phase separation tower 5 for separating a phenol sodium salt aqueous solution produced by a reaction kettle 4 from a synergistic extractant, and an extractant storage tank 6, wherein the first extraction tower 1 is communicated with the second extraction tower 2, the second extraction tower 2 is communicated with the rectification tower 3, the back-extraction kettle 4 and the extractant storage tank 6, the rectification tower 3 is communicated with the back-extraction kettle 4 and the extractant storage tank 6, the back-extraction kettle 4 is communicated with the phase separation tower 5, and the phase separation tower 5 is communicated with the extractant storage tank 6.
The invention relates to a method for treating phenol-ammonia wastewater, which comprises the following steps:
step 1: uniformly mixing an alkaline amine extractant, a neutral phosphorus-containing extractant, an acidic adjuvant and a main extractant to obtain an organic phase, and mixing the organic phase with the acidic adjuvant to obtain a synergistic extractant A;
step 2: and adding the phenol-ammonia wastewater mixture B to be separated and the main extracting agent F into a first extraction tower for separation to obtain a phenol-ammonia extraction phase G and a phenol-ammonia solution C, conveying the phenol-ammonia extraction phase G from the top of the first extraction tower to a phenol removing tower, and outputting the phenol-ammonia solution C from the bottom of the first extraction tower to a second extraction tower. In step 2 in this embodiment, before entering the first extraction tower, the phenol-ammonia wastewater mixture B to be separated reacts with alkali in a deamination tower to perform deamination; the main extractant F is mainly one of diisopropyl ether and methyl isobutyl ketone, and is prepared according to a DIPE system: the organic phase extractant is diisopropyl ether, and the water phase is phenol ammonia water solution. The system preferentially extracts unit phenol in the water phase, and the polyphenol residue is more; MIBK extractant: the effect of methyl isobutyl ketone on treating the wastewater is better than that of diisopropyl ether, but the COD and the polyphenol content in the treated wastewater are still about 800mg/L, and the separation effect is poor. By reasonably controlling the ratio of the phenol and the polyhydric phenol, most of the phenol unit is extracted into the main extracting agent, and a small amount of phenol unit and a large amount of polyhydric phenol enter the second extracting tower.
And step 3: extracting the synergistic extraction agent A obtained in the step 1 and the phenol ammonia solution C obtained in the step 2 in a second extraction tower to obtain an organic phase D of phenol ammonia and dephenolized wastewater H; the principles involved in the above separation process include: the method is characterized in that lone-pair electrons of neutral phosphorus-containing extractant P ═ O group O and lone-pair electrons of basic amine extractant N are coordinated with central phenoxide anions of an electric neutral ligand consisting of phenoxide anions, acid radical ions and hydrogen ions to form an extraction compound, so that phenols are extracted into an organic phase.
And 4, step 4: separating the organic phase D of the phenol ammonia in a rectifying tower to obtain a main extracting agent F and a mixture E at the bottom of the rectifying tower;
and 5: and (3) mixing the mixture E obtained in the step (4) with a stripping agent I in a stripping kettle to generate a sodium phenolate aqueous solution M and a synergistic extraction agent A, introducing the generated sodium phenolate aqueous solution M and the synergistic extraction agent A into a phase separation tower, and separating the sodium phenolate aqueous solution M and the synergistic extraction agent A, wherein the synergistic extraction agent A enters an extraction agent recovery storage tank, and the synergistic extraction agent in the extraction agent recovery storage tank can enter a second extraction tower, so that the recycling of the extraction agent is realized.
Through the steps, the unit phenol can be extracted by the first extraction tower, the polyhydric phenol can be extracted by the second extraction tower, and the unit phenol and the polyhydric phenol are separated in the rectifying tower and the back extraction kettle, so that the technical effect of respectively extracting the unit phenol and the polyhydric phenol is realized.
In a preferred embodiment, in the step 1, the reaction temperature of the organic phase and the acidic adjuvant is: mixing at 40-55 deg.C for 5-15 min; the preferred mixing temperature is 45 ℃ and the mixing time is 10 min;
in the step 2, the volume ratio of the phenol-ammonia wastewater mixture B to be separated to the main extracting agent is as follows: 3-5: 1, wherein the corresponding extraction temperature is 35-50 ℃, the extraction time is 10-30 min, the preferred extraction temperature is 45 ℃, and the reaction time is 15 min;
in the step 3, the volume ratio of the synergistic extraction agent A to the phenol ammonia solution C is 50-90:50-10, the corresponding extraction temperature is 35-55 ℃, the reaction time is 5-25 min, the preferable reaction temperature is 50 ℃, and the reaction time is 10min
In said step 4, the rectification column is operated at a pressure of 65 to 130Kpa, preferably at an operating pressure of 105 Kpa;
in the step 5, the volume ratio of the mixture E to the stripping agent is 1: 2-1: 4.
Preferably, in the step 2, the phenol-ammonia wastewater mixture B to be separated is a solution containing both phenols and salt wastewater ions, the concentration of the phenols in the phenol-ammonia wastewater mixture B to be separated is 1000mg/L to 20000mg/L, and the concentration of ammonium ions is 30mg/L to 200 mg/L; (ii) a Phenols in the phenol-ammonia wastewater mixture B to be separated comprise phenol, thymol, 3, 4-dimethylphenol, isopropyl phenol, methyl phenol, dimethyl phenol, naphthol, anthranilic phenol, phloroglucinol, hydroquinone, phloroglucinol, 3-ethylphenol, pyridine, methylpyridine, propionitrile, butyronitrile, hydrogen sulfide, carbon dioxide and the like, and mainly come from condensates obtained after coal pyrolysis;
in the step 5, the stripping agent is selected from an alkaline solution, the alkaline in the alkaline solution is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia water and magnesium hydroxide, and the concentration of the solution is between 5% and 25%, such as 5%, 10%, 15%, 20%, 25%, etc., preferably 20%.
Examples
In the following examples, the concentration of dilute sulfuric acid used was 20%, and all the concentration was performed in a first extraction flask, which corresponds to one theoretical stage of extraction.
Example 1
The synergistic extraction agent consists of 98 vol% of diisopropyl ether, 0.4 vol% of dodecylamine, 1.5 vol% of tributyl phosphate and 0.1% of dilute sulfuric acid (the concentration is 20%), the synergistic extraction agent reacts with the main extraction agent at 40 ℃ for 5min, after the phenol-ammonia wastewater mixture B to be separated is subjected to primary extraction in a first extraction tower by utilizing diisopropyl ether, the content of total phenols in a phenol-ammonia solution C is 1100mg/L and COD is 5500mg/L, the synergistic extraction agent and the phenol-ammonia wastewater mixture B to be separated are extracted and separated according to the volume ratio of 1:5 at 45 ℃ for 10min, the content of total phenols in dephenolized wastewater H is reduced to 575mg/L, and the biochemical degradability is obviously improved; by calculation, the extraction rate of phenols by the extractant was 47.7%, and the separation coefficient of phenols from water was 1.91.
Example 2
The synergistic extractant consists of 97.9 vol% of methyl isobutyl ketone, 0.1 vol% of hexadecylamine, 1.85 vol% of tributyl phosphate and 0.15 vol% of acidic auxiliary agent; after methyl isobutyl ketone is used for primary extraction in a first-stage extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 1265mg/L, the oil content is 1032mg/L, the COD is 6500mg/L, the synergistic extraction agent and the phenol-ammonia wastewater mixture B to be separated are extracted and separated in a second extraction tower at the temperature of 45 ℃ for 12min according to the volume ratio of 1:3, the content of the total phenols in the dephenolized wastewater H is reduced to 456mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of phenols by the extractant was 63.7%, and the separation coefficient of phenols from water was 2.75.
Example 3
The synergistic extractant consists of 96 vol% of methyl isobutyl ketone, 2 vol% of octadecylamine, 1.95 vol% of tributyl phosphate and 0.05 vol% of dilute sulfuric acid; after methyl isobutyl ketone is subjected to primary extraction in a first-stage extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 965mg/L, the oil content is 887mg/L, the COD is 4500mg/L, the volume ratio of the synergistic extractant to the phenol-ammonia wastewater mixture B to be separated is 1:6, after extraction and separation, the content of total phenols in the dephenolized wastewater H is reduced to 377mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of the phenol by the extractant is 60.9%, and the phenol separation coefficient is 2.55.
Example 4
The synergistic extractant consists of 99.7 vol% of methyl isobutyl ketone, 0.1 vol% of hexadecylamine and 0.2 vol% of tributyl phosphate; after methyl isobutyl ketone is subjected to first-stage extraction in a first-stage extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 1265mg/L, the oil content is 887mg/L, the COD is 4500mg/L, the volume ratio of the synergistic extraction agent to the phenol-ammonia wastewater mixture B to be separated is 1:3, after extraction separation is carried out in a second extraction tower at 45 ℃ for 12min, the content of total phenols in the dephenolized wastewater H is reduced to 617mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of the phenol by the extractant was 51.2%, and the phenol separation coefficient was 2.04.
Example 5
The synergistic extractant consists of 93 vol% of methyl isobutyl ketone, 0.1 vol% of hexadecylamine, 6.75 vol% of tributyl phosphate and 0.15 vol% of dilute sulfuric acid; after methyl isobutyl ketone is subjected to first-stage extraction in a first-stage extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 1265mg/L, the oil content is 887mg/L, the COD is 4500mg/L, the volume ratio of the synergistic extraction agent to the phenol-ammonia wastewater mixture B to be separated is 1:3, after extraction separation is carried out in a second extraction tower at 45 ℃ for 12min, the content of total phenols in the dephenolized wastewater H is reduced to 310mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of the phenol by the extractant was 75.3%, and the phenol separation coefficient was 4.05.
Example 6
The synergistic extractant consists of 96 vol% of methyl isobutyl ketone, 0.1 vol% of hexadecylamine, 3.75 vol% of tributyl phosphate and 0.15 vol% of dilute sulfuric acid; after methyl isobutyl ketone is subjected to first-stage extraction in a first-stage extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 1256mg/L, the oil content is 887mg/L, the COD is 4500mg/L, the volume ratio of the synergistic extraction agent to the phenol-ammonia wastewater mixture B to be separated is 1:3, after extraction separation is carried out in a second extraction tower at 45 ℃ for 12min, the content of total phenols in the dephenolized wastewater H is reduced to 420mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of the phenol by the extractant is 66.8%, and the phenol separation coefficient is 3.01.
Example 7
The synergistic extractant consists of 97.9 vol% of methyl isobutyl ketone, 0.5 vol% of hexadecylamine, 1.45 vol% of tributyl phosphate and 0.15 vol% of dilute sulfuric acid; after methyl isobutyl ketone is subjected to first-stage extraction in a first-stage extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 1265mg/L, the oil content is 887mg/L, the COD is 4500mg/L, the volume ratio of the synergistic extraction agent to the phenol-ammonia wastewater mixture B to be separated is 1:3, after extraction separation is carried out in a second extraction tower at 45 ℃ for 12min, the content of total phenols in the dephenolized wastewater H is reduced to 398mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of the phenol by the extractant was 68.5%, and the phenol separation coefficient was 3.17.
Example 8
The synergistic extractant consists of 97.9 vol% of methyl isobutyl ketone, 1 vol% of hexadecylamine, 1 vol% of tributyl phosphate and 0.1 vol% of dilute sulfuric acid; after methyl isobutyl ketone is subjected to first-stage extraction in a first-stage extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 1265mg/L, the oil content is 887mg/L, the COD is 4500mg/L, the volume ratio of the synergistic extraction agent to the phenol-ammonia wastewater mixture B to be separated is 1:3, after extraction separation is carried out in a second extraction tower at 45 ℃ for 12min, the content of total phenols in the dephenolized wastewater H is reduced to 362mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of phenols by the extractant was 71.4%, and the phenol separation coefficient was 3.49.
Example 9
The synergistic extractant consists of 97.9 vol% of methyl isobutyl ketone, 1.5 vol% of hexadecylamine, 0.5 vol% of tributyl phosphate and 0.1 vol% of dilute sulfuric acid; after methyl isobutyl ketone is subjected to first-stage extraction in a first-stage extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 1265mg/L, the oil content is 887mg/L, the COD is 4500mg/L, the volume ratio of the synergistic extraction agent to the phenol-ammonia wastewater mixture B to be separated is 1:3, after extraction separation is carried out in a second extraction tower at 45 ℃ for 12min, the content of total phenols in the dephenolized wastewater H is reduced to 312mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of the phenol by the extractant is 75.3%, and the phenol separation coefficient is 4.04.
Example 10
The synergistic extractant consists of 93.9 vol% of methyl isobutyl ketone, 1.95 vol% of hexadecylamine, 4 vol% of tributyl phosphate and 0.15 vol% of dilute sulfuric acid; after methyl isobutyl ketone is subjected to first-stage extraction in a first-stage extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 1265mg/L, the oil content is 887mg/L, the COD is 4500mg/L, the volume ratio of the synergistic extraction agent to the phenol-ammonia wastewater mixture B to be separated is 1:3, after extraction separation is carried out in a second extraction tower at 45 ℃ for 12min, the content of total phenols in the dephenolized wastewater H is reduced to 280mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of phenols by the extractant was 77.9%, and the phenol separation coefficient was 4.33.
Example 11
The synergistic extraction agent consists of 97 vol% of methyl isobutyl ketone, 0.2 vol% of trioctylamine, 2.6 vol% of tributylphosphine oxide and 0.2 vol% of dilute sulfuric acid, after the methyl isobutyl ketone is subjected to primary extraction in a primary extraction tower, the content of total phenols in the phenol-ammonia solution C is reduced to 1265mg/L, the content of oil is 887mg/L and the COD is 4500mg/L, the volume ratio of the synergistic extraction agent to the phenol-ammonia wastewater mixture B to be separated is 1:5, after extraction separation is carried out in a second extraction tower at 45 ℃ for 12min, the content of total phenols in the dephenolized wastewater H is reduced to 388mg/L, and the biodegradability is obviously improved; by calculation, the extraction rate of the phenol by the extractant was 69.3%, and the phenol separation coefficient was 3.26.
Example 12
The synergistic extraction agent consists of 92 vol% of diisopropyl ether, 0.15 vol% of piperazine, 7.35 vol% of tributyl phosphate and 0.5 vol% of dilute sulfuric acid, the content of total phenols in the phenol-ammonia solution C is reduced to 1265mg/L, the content of oil is 887mg/L and the COD is 4500mg/L after the first-stage extraction of methyl isobutyl ketone in a first-stage extraction tower, the volume ratio of the synergistic extraction agent to the phenol-ammonia wastewater mixture B to be separated is 1:6, after extraction separation is carried out in a second extraction tower at 45 ℃ for 12min, the content of total phenols in the dephenolized wastewater H is reduced to 337mg/L, and the biochemical degradability is obviously improved; by calculation, the extraction rate of the phenol by the extractant was 73.4%, and the phenol separation coefficient was 3.76.
Comparative example
Taking example 2 as an example, the following comparative examples were set up:
comparative example 1: the difference from example 2 is that the basic amine extractant and the acidic adjuvant are not contained, and the basic amine extractant is replaced by the same amount of neutral phosphorus-containing extractant as in example 2. The extraction rate of phenols by the extractant was 20.5% and the separation coefficient was 1.26.
Comparative example 2: the difference from example 2 is that no neutral phosphorus-containing extractant is included, and that part of the neutral phosphorus-containing extractant is replaced by the same amount of the same basic amine-based extractant as in example 2. The extraction rate of phenols by this extraction agent was found to be 42.6% by calculation, and the separation coefficient was found to be 1.74.
Comparative example 3: the difference from example 2 is that no acidic adjuvant is contained and this part of the acidic adjuvant is replaced by the same amount of the same neutral phosphorus-containing extractant as in example 2. The extraction rate of phenols by the extractant was found to be 31.5% by calculation, and the separation coefficient was found to be 1.46.
In this embodiment, phenol ammonia wastewater mixture B to be separated can extract 90% of unit phenol, 10% of polyhydric phenol in first extraction tower, and 90% of polyhydric phenol can enter into the second extraction tower, because the proportion of unit phenol is very low in the second extraction tower, can not effectively extract, therefore in the second extraction tower, the synergistic extractant can extract mostly the polyhydric phenol, can realize effectively separating unit phenol, polyhydric phenol through first extraction tower, second extraction tower like this. The above examples and the analysis of the comparison document show that the synergistic extractant can effectively improve the extraction efficiency of the polyphenol, wherein the proportion of the alkaline amine extractant is reduced, the proportion of the neutral phosphorus-containing extractant and the acidic auxiliary agent is improved, and the separation effect of the phenols can be improved. The extraction effect is enhanced along with the increase of the PH value; neutral phosphorus extractants can enhance the extraction effect, but are high in price and need to be used in a proper amount. The preferred synergistic extractant combination of the invention is: 93 vol% of methyl isobutyl ketone, 0.1 vol% of hexadecylamine, 6.75 vol% of tributyl phosphate and 0.15 vol% of dilute sulfuric acid; 97.9 vol% of methyl isobutyl ketone, 1.5 vol% of hexadecylamine, 0.5 vol% of tributyl phosphate and 0.1 vol% of dilute sulfuric acid; 93.9 vol% of methyl isobutyl ketone, 1.95 vol% of hexadecylamine, 4 vol% of tributyl phosphate and 0.15 vol% of dilute sulfuric acid. The extraction rate of the synergistic extractant combination is up to more than 75%, the extraction effect is good, the expected effect can be achieved by using less alkaline amine extractants and neutral phosphorus-containing extractants, and the cost is greatly reduced. The synergistic extraction agent is used for extracting phenol-ammonia wastewater according to the extraction method provided by the application, so that higher phenol extraction rate and high phenol separation efficiency can be obtained.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. An extracting agent for treating phenol-ammonia wastewater is characterized by comprising the following components in percentage by volume: 0.1 to 3 percent of alkaline amine extractant, 0.1 to 5 percent of neutral phosphorus-containing extractant and 92 to 99.79 percent of main extractant.
2. The extractant for treating phenol-ammonia wastewater of claim 1, wherein the main extractant is selected from at least one of ethyl acetate, butanol, heptane, octane, methyl isobutyl ketone and diisopropyl ether;
the alkaline amine extractant is selected from at least one of dodecylamine, hexadecylamine, piperazine, octadecylamine, N-ethylpiperazine and methylpiperazine.
3. The extractant for treating phenol-ammonia wastewater of claim 1, wherein the neutral phosphorus-containing extractant has a structure of
Wherein K2, K3 and K4 are independently selected from any one of a linear or branched alkyl group having 2 to 8 carbon atoms, a linear or branched alkoxy group having 4 to 8 carbon atoms, wherein at least two of K2, K3 and K4 are the same.
4. The extraction agent for treating phenol-ammonia wastewater as claimed in claim 3, wherein the neutral phosphorus-containing extraction agent is at least one selected from the group consisting of phosphoric acid triesters, monoalkyl phosphoric acid diesters, dialkyl phosphoric acid monoesters, and trialkyl phosphorus oxides.
5. The extractant for treating phenol-ammonia wastewater of any one of claims 1 to 4, further comprising 0.01 to 1% (by volume percentage) of an acidic adjuvant selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, thiocyanic acid, perchloric acid, cinnamic acid, naphthenic acid, acetic acid, glutamic acid, tartaric acid, citric acid, glycolic acid, and ethylenediaminetetraacetic acid.
6. A method for treating phenol-ammonia wastewater, characterized by comprising the steps of:
step 1: uniformly mixing an alkaline amine extractant, a neutral phosphorus-containing extractant, an acidic adjuvant and a main extractant to obtain an organic phase, and mixing the organic phase with a pre-saturated solution acidic adjuvant to obtain a synergistic extractant A;
step 2: adding the phenol-ammonia wastewater mixture B to be separated and a main extracting agent F into a first extraction tower for separation to obtain a phenol-ammonia extraction phase G and a phenol-ammonia solution C;
and step 3: extracting the synergistic extraction agent A obtained in the step 1 and the phenol ammonia solution C obtained in the step 2 in a second extraction tower to obtain an organic phase D of phenol ammonia and dephenolized wastewater H;
and 4, step 4: separating the organic phase D of the phenol ammonia in a rectifying tower to obtain a main extracting agent F and a mixture E at the bottom of the rectifying tower;
and 5: and (4) mixing the mixture E obtained in the step (4) with a stripping agent I in a stripping kettle to generate a sodium phenolate aqueous solution M and a synergistic extraction agent.
7. The method for treating phenol-ammonia wastewater according to claim 6,
in the step 2, the volume ratio of the phenol-ammonia wastewater mixture B to be separated to the main extracting agent is as follows: 3: 1-7: 1;
in the step 3, the volume ratio of the organic phase feed liquid A to the phenol ammonia solution C is 50-90: 50-10;
in the step 5, the volume ratio of the mixture E to the stripping agent is 1: 1-1: 4.5.
8. The method for treating phenol-ammonia wastewater according to claim 6,
in the step 1, the reaction temperature of the organic phase and the acidic auxiliary agent is 40-55 ℃, and the extraction time is 10-15 min;
in the step 4, the pressure of the rectifying tower operation is 105-130 KPa.
9. The method for treating phenol-ammonia wastewater according to claim 6,
in the step 2, the phenol-ammonia wastewater mixture B to be separated is a solution containing phenols and salt wastewater ions, and the concentration of phenols in the phenol-ammonia wastewater mixture B to be separated is 1000mg/L-20000 mg/L;
in the step 5, the stripping agent is selected from an alkali solution, and the alkali in the alkali solution is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia water and magnesium hydroxide.
10. The method for treating phenol-ammonia wastewater in claim 6, wherein in the step 2, the phenol-ammonia wastewater mixture B to be separated is subjected to a deamination process by reacting with alkali before entering the first extraction tower.
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