CN110746527B - Treatment method of (methyl) acrylic acid wastewater - Google Patents
Treatment method of (methyl) acrylic acid wastewater Download PDFInfo
- Publication number
- CN110746527B CN110746527B CN201911095366.0A CN201911095366A CN110746527B CN 110746527 B CN110746527 B CN 110746527B CN 201911095366 A CN201911095366 A CN 201911095366A CN 110746527 B CN110746527 B CN 110746527B
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- wastewater
- methyl
- vinyl monomer
- methacrylic acid
- 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.)
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Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 72
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000011282 treatment Methods 0.000 title description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 52
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- CARNFEUGBMWTON-UHFFFAOYSA-N 3-(2-prop-2-enoxyethoxy)prop-1-ene Chemical compound C=CCOCCOCC=C CARNFEUGBMWTON-UHFFFAOYSA-N 0.000 claims description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical group CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims 2
- 150000001409 amidines Chemical class 0.000 claims 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 claims 1
- 229920000151 polyglycol Polymers 0.000 claims 1
- 239000010695 polyglycol Substances 0.000 claims 1
- -1 acrylic ester Chemical class 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000005286 illumination Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- 238000010521 absorption reaction Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000002745 absorbent Effects 0.000 description 12
- 239000002250 absorbent Substances 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000012986 chain transfer agent Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PQHKBJOUOHLCCV-UHFFFAOYSA-N CC1(C=CC=CC1C(=O)C2=CC=C(C=C2)OCCO)O Chemical compound CC1(C=CC=CC1C(=O)C2=CC=C(C=C2)OCCO)O PQHKBJOUOHLCCV-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PNTLMFABGCHLMN-UHFFFAOYSA-N [4-(2-hydroxyethoxy)phenyl]-phenylmethanone Chemical compound C1=CC(OCCO)=CC=C1C(=O)C1=CC=CC=C1 PNTLMFABGCHLMN-UHFFFAOYSA-N 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- CQNUMTMWJRSIRY-UHFFFAOYSA-N 1,1'-biphenyl;diphenylmethanone Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 CQNUMTMWJRSIRY-UHFFFAOYSA-N 0.000 description 1
- POJPQMDDRCILHJ-UHFFFAOYSA-N 1,1,1,2,2,2-hexabromoethane Chemical compound BrC(Br)(Br)C(Br)(Br)Br POJPQMDDRCILHJ-UHFFFAOYSA-N 0.000 description 1
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- NIWFIJFHALTBRN-UHFFFAOYSA-N 2-methyl-5-propan-2-ylidenecyclopentan-1-one Chemical compound CC1CCC(=C(C)C)C1=O NIWFIJFHALTBRN-UHFFFAOYSA-N 0.000 description 1
- UVSYLHMNAUJEFX-UHFFFAOYSA-N 2-sulfanylbutan-1-ol Chemical compound CCC(S)CO UVSYLHMNAUJEFX-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- IPGWRAMHLWMBNJ-UHFFFAOYSA-N 4-hydroxyfluoren-1-one Chemical compound OC=1C=CC(C2=CC3=CC=CC=C3C12)=O IPGWRAMHLWMBNJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001284 azanium sulfanide Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- CXAYOCVHDCXPAI-UHFFFAOYSA-N naphthalen-1-yl(phenyl)methanone Chemical compound C=1C=CC2=CC=CC=C2C=1C(=O)C1=CC=CC=C1 CXAYOCVHDCXPAI-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Abstract
The invention discloses a method for treating (methyl) acrylic acid wastewater, which comprises the steps of adding vinyl monomers and an initiator into the (methyl) acrylic acid wastewater, converting the vinyl monomers and the initiator into a gel-form polymer by using illumination, and dehydrating and drying the polymer to obtain a high-hydroscopicity material. The method for treating the acrylic acid wastewater has the advantages of low energy consumption, high efficiency and simple process, and can recycle the wastewater produced by (methyl) acrylic ester.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for treating acrylic acid wastewater.
Background
The (methyl) acrylic acid contained in the industrial wastewater generated in the production of (methyl) acrylic esters is difficult to biodegrade, the treatment cost of a direct incineration method is too high, and the water environment is greatly destroyed after dilution and discharge, so that harmless treatment is required. The treatment methods for (meth) acrylic acid-based wastewater, including three of physical, chemical and biological methods, require multi-step treatments that are time-consuming and costly to operate.
The prior treatment mode, the application number is CN201710930729.2 and the application date is 20171009, discloses a comprehensive treatment method of acrylic ester production wastewater, which comprises the steps of adding at least one chain transfer agent of aliphatic mercaptan, carbon tetrachloride, sodium formate, inorganic phosphate, octanol, isopropanol, propanol or butanol, adding at least two free radical initiators of ammonium persulfate, sodium persulfate, potassium persulfate, sodium bisulfate, ammonium bisulfide, potassium bisulfide, hydrogen peroxide, ferrous chloride, cumene hydroperoxide or benzoyl peroxide, carrying out polymerization reaction for 4-9 hours at 45-85 ℃, filtering by using a nanofiltration/ultrafiltration membrane, or adding an organic solvent to separate out a polymer, filtering and separating the obtained solid to serve as a scale inhibitor, redistilling an organic solvent in a liquid part, and concentrating and incinerating the rest wastewater. However, the polyacrylic acid obtained by the chemical treatment has low molecular weight, and the wastewater is difficult to separate.
Further, the invention patent with the application number of CN201510595251.3 and the application date of 20150917 discloses a method for treating acrylic acid ester wastewater by photocatalysis, which adopts a high-pressure mercury lamp or a KrF ultraviolet excimer laser with the main wavelength of 254nm to radiate the treated wastewater with persulfate or hydrogen peroxide, then a polyvalent metal ion compound is added as a precipitant to flocculate the polymer of acrylic acid in the wastewater, and then the precipitate is filtered, wherein the removal rate of the acrylic acid in the wastewater is about 77-88 percent. Although the treatment process is greatly simplified, the acrylic acid of the wastewater is not recycled.
Disclosure of Invention
The invention aims at: aiming at the problems, the invention provides a (methyl) acrylic acid wastewater treatment method which has low energy consumption, high efficiency and simple process, adopts photopolymerization to convert methacrylic acid, acrylic acid, methacrylic acid salt or acrylic acid salt in the (methyl) acrylic acid wastewater into a gel-form polymer, and then obtains the super absorbent resin through dehydration and drying, thereby being used as a moisture-keeping, water-absorbing and water-proof super absorbent material in the aspects of environmental protection, agriculture, forestry and the like.
The technical scheme adopted by the invention is as follows:
the method for treating (methyl) acrylic acid wastewater comprises the following steps:
A. adding vinyl monomer and photoinitiator into (methyl) acrylic acid wastewater to obtain solution;
B. initiating polymerization by irradiating the solution with light to obtain a gel polymer with high water absorption characteristics;
C. the polymer was separated.
In the above method, the (meth) acrylic acid waste water in the step A refers to the fractional waste water generated during the acrylic acid or methacrylic acid esterification reaction, and the washing liquid generated by washing the esterification reaction product with caustic soda, sodium carbonate or potassium hydroxide solution, wherein the washing liquid mainly contains one or more of methacrylic acid, acrylic acid, methacrylic acid salt or acrylic acid salt, and the methacrylic acid salt or acrylic acid salt mainly refers to the sodium salt or potassium salt thereof. The waste water contains, in addition to methacrylic acid, acrylic acid, methacrylic acid salts or acrylic acid salts, catalysts, stabilizers, starting alcohols and the product (meth) acrylic acid esters for the esterification reaction, and has a complex composition. The direct thermal polymerization, such as the methods disclosed in the above section, produces little gel, is difficult to separate directly, and the product does not have high water absorption, and is not a useful high water absorption material. The applicant finds that methacrylic acid, acrylic acid, methacrylic acid salt and acrylic acid salt in the wastewater can be conveniently and efficiently converted into gel products by adopting a photopolymerization method, and the gel products are dehydrated and dried to form the super absorbent resin which can be used as super absorbent materials, and water produced by dehydration and drying can be returned to production for use, so that harmless and recycling treatment and use of the wastewater are realized.
The photoinitiator is a photoinitiator which generates free radicals after illumination, and comprises: aryl ketones, such as substituted and unsubstituted benzophenones, for example: 4-hydroxybenzophenone, 4- (2-hydroxyethyl) -oxybenzophenone, 4-hydroxyfluorenone, 4- (2-hydroxyethyl) -oxybenzophenone, biphenyl benzophenone, fluorenone, naphthyl phenyl ketone, camphorone, thioxanthone, and the like; substituted and unsubstituted benzoin ethers, 2-hydroxy-2-methyl-1-phenyl-propanone-1, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-dimethoxy-, 2-diphenylethan-1-one, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylbenzophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, and the like, and combinations thereof. The photoinitiator may be dissolved in the vinyl monomer or a small amount of solvent, such as ethanol, acetone, etc., before being added to the photopolymerization solution. Preferably, the photoinitiator sensitive to the wavelength range of 280-410nm is used in an amount of 0.08-2 w% of the wastewater mass.
Further, the content of methacrylic acid, acrylic acid, methacrylic acid salt or acrylic acid salt in the (meth) acrylic acid wastewater is 1 to 20w% of the mass of the aqueous solution, and the content of methacrylic acid, acrylic acid, methacrylic acid salt or acrylic acid salt varies greatly depending on the production process and the raw materials used in the esterification reaction. The water absorption property is regulated or improved by adding the vinyl monomer with similar properties, particularly water-soluble vinyl monomer, so that the photopolymerization reaction of methacrylic acid, acrylic acid, methacrylic acid salt or acrylic acid salt of the wastewater can be promoted, and particularly when the content of the methacrylic acid, acrylic acid, methacrylic acid salt or acrylic acid salt of the wastewater is small, for example, lower than 3w percent, the gel polymer obtained by adding the vinyl monomer is easier to separate and has better water absorption property. Suitable vinyl monomers include monofunctional monomers such as acrylamide, acrylic acid and salts thereof, methacrylic acid and salts thereof, vinyl and substituted vinyl sulfonic acids and salts thereof; a small amount of a polyfunctional vinyl monomer may also be added to regulate the degree of crosslinking of the resulting polymer, such as methylenebisacrylamide, ethyleneglycol diallyl ether, butyleneglycol diallyl ether, polydiol diallyl ether, trimethylol propane triallyl ether, ethoxylated trimethylol propane triallyl ether, and the like. The consumption of the monofunctional vinyl monomer can reach 0-30w%, preferably 0-20w% of the wastewater, and the utilization value of methacrylic acid, acrylic acid, methacrylic acid salt and acrylic acid salt in the wastewater is low due to excessive addition; the amount of the polyfunctional monomer used should not be too large, otherwise the water absorption of the product is affected, and the amount is preferably 0 to 5w% of the amount of the waste water.
Preferably, the waste water and the aqueous solution after adding vinyl monomers, particularly acrylic acid or methacrylic acid, can be neutralized with alkali liquor to make the pH value of the waste water between 4 and 10 and the neutralization degree of the waste water more than 60%, so as to reduce the corrosiveness of the waste water to equipment, and adjust and control the water absorption rate and the water absorption speed of the obtained polymer as the super absorbent resin.
Further, since the photopolymerization reaction is fast, the temperature of the system increases as the polymerization reaction proceeds, and the photopolymerization and the thermal polymerization can be combined and sequentially performed, thereby increasing the degree of the polymerization reaction. In one embodiment, the photoinitiator and the thermal initiator are added simultaneously, the polymerization heat of the photopolymerization reaction is utilized to automatically raise the temperature of the system, and the thermal initiator is started to initiate the polymerization of the rest monomers, so that the conversion rate of methacrylic acid, acrylic acid, methacrylic acid salt, acrylic acid salt and the added vinyl monomers in the system is improved. Water-soluble thermal initiators may be used, including persulfates, such as ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and water-soluble azo initiators, such as the agents azobisisobutylamidine hydrochloride, azobisiso Ding Mi hydrochloride, azobiscyanopentaoic acid, azobisisopropylimidazoline. For persulfates and hydrogen peroxide, reducing agents may also be used in combination to properly reduce the onset temperature of the initiator, and useful reducing agents include sulfite and ferrous chloride, etc., the methods of use and amounts of which can be queried by those skilled in the art from the relevant information.
Further, the light source used for the light irradiation initiation polymerization includes UV lamp, LED lamp, etc., including polar and electrodeless mercury lamp, low-pressure fluorescent lamp, moth-killing lamp, bactericidal lamp, plate burning lamp, etc., preferably UV lamp or LED lamp with emission wavelength of 280-415 nm. As a preferred embodiment, inert gases such as nitrogen, argon and the like can be introduced before illumination to remove oxygen, so that the oxygen content in the solution is lower than 100ppm, particularly lower than 50ppm, and methacrylic acid, acrylic acid, methacrylic acid salt or acrylic acid salt and the like in the wastewater are polymerized by illumination.
In summary, the advantages of the treatment method of (meth) acrylic acid wastewater of the present invention are manifold:
1. the photopolymerization is carried out instead of heating to decompose the thermal initiator to initiate the polymerization, so that the efficiency is high, the operation is convenient, the heating step is omitted, the energy consumption is saved, the wastewater treatment cost is reduced, and the energy-saving effect is very obvious especially when a large amount of (methyl) acrylic acid wastewater is treated;
2. the photopolymerization is fast, usually completed in tens of seconds to minutes, and has high efficiency, and the conversion rate of methacrylic acid, acrylic acid, methacrylic acid salt or acrylic acid salt in the wastewater is high;
3. the photopolymerization treatment process of the wastewater is easy to control, and the product is gel and is convenient to separate;
4. the polymerization product obtained by photopolymerization has high water absorption property, the water absorption multiplying power is larger than 30, and the polymerization product can be used as a water-retaining material and a water-absorbing material, realizes the resource utilization of wastewater, and can be used as a water-retaining agent for agricultural planting, soil improvement, road slope treatment, water prevention, leakage stoppage and the like.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
All 3 of the wastewater used in the examples below were from a chemical plant for producing (meth) acrylic acid ester, the sodium acrylate content of wastewater 1 was about 14.3w%, the COD value was 104000, the pH value was 10, the acrylic acid content of wastewater 2 was about 1.2w%, the COD value was about 9000, and the pH value was less than 2; the sodium methacrylate content of the wastewater 3 is about 16w%, the COD value is about 110000, and the pH value is 9; and the consumption of the waste water 1, the waste water 2 and the waste water 3 is 100 g.
Example 1
In this example, using wastewater 1, a 250ml three-necked flask equipped with an electric stirrer, a thermometer and a nitrogen inlet/outlet tube was placed in a water bath, and wastewater 1 and 0.1 g of a photoinitiator 2959 (1 w%) were added, stirred, and bubbled with nitrogen for 15 minutes. The gel was taken out and dried in an oven at 120℃to give 16 g of a hard block having a water content of about 10 w%. The resultant powder was pulverized into fine powder by an electric pulverizer, and the water absorption rate for pure water was 36 times as measured by a standard method.
Example 2
In this example, waste water 1 was used, 10w% AA, 0.08w% photoinitiator 819 and 0.2w% hydroxybenzophenone were added, the pH was adjusted to about 8 with alkaline water, the led was illuminated for 120 seconds, and the remainder was dried to give about 32 grams of solids having a water content of about 10w% and a water absorption of 112 times.
Example 3
This example uses wastewater 1, 20w% AA, sodium methallyl sulfonate 2w%, pH adjusted with KOH to about 4,0.1w% 2959 and 0.3w% azobisisobutylamidine hydrochloride. The LED was left to stand in a water bath at 80 c for 4 hours after 60 seconds of illumination. The drying treatment similar to example 1 gave a water content of about 10w% solids of 47 g and a water absorption of 500 times.
Example 4
In this example, waste water 2 was used, AA20w% and ethylene glycol diallyl ether 5%,0.26 g of thioglycollic acid (1 w% of the monomer amount) were added, the pH was adjusted to about 10 with alkali water, a gel-like product was obtained by irradiation of a medium-pressure mercury lamp for 180 seconds with 0.1w% of a photoinitiator 819 and 2w% of hydroxybenzophenone, 60ml of acetone was added and stirred, and after water was squeezed out, 40 g of a solid having a water content of about 10w% was obtained by drying, and the water absorption was 67 times.
Example 5
This example uses waste water 2, AAw10%, 0.2w% methylene bisacrylamide and 0.4w% 2959, and the pH was adjusted to about 3 with alkaline water, and the gel-like product was obtained by irradiation with a medium-pressure mercury lamp for 180 seconds, and 17 g of a solid having a water content of about 10w% and a water absorption of 55 times was obtained after the drying treatment similar to example 1.
Example 6
This example uses wastewater 3, 10w% AA, 0.1w% 2959, adjusted to a pH of about 8 with alkaline water, led illuminated for 120 seconds, and the remainder was dried to give about 36 grams of solids with a water content of about 10w% and a water absorption of 58 times.
Example 7
This example was used as a comparative example, a 250ml three-necked flask equipped with an electric stirrer, a thermometer and a nitrogen inlet/outlet tube was put into a water bath, 100 g of wastewater 1 and 0.1 g of potassium persulfate as a thermal initiator were added, stirred and bubbled with nitrogen for 15 minutes, after reacting in the water bath at 80℃for 3 hours and at 88℃for 3 hours, the material in the flask was still a transparent aqueous solution sample, the solution was poured into 200ml of ethanol, the precipitated gel was separated out, 8 g of solid was obtained after drying, it was pulverized into fine powder by an electric pulverizer, the water absorption to pure water was measured to be about 1.5 times according to a standard method, most of the powder was dissolved in water, and the remaining portion was re-dried and then weighed about 2 g.
The vinyl monomer Acrylic Acid (AA), sodium methallylsulfonate, methylenebisacrylamide, ethylene glycol diallyl ether, naOH or KOH, photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylbenzophenone (abbreviated as 2959), 4-hydroxybenzophenone, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide (abbreviated as 819), azo initiator azo diisobutylamidine hydrochloride (AIBA) which is a water-soluble thermal initiator, potassium persulfate, thioglycollic acid, isopropanol, etc. are commercially available; and the photopolymerized lamp source is a 1000W medium pressure mercury lamp or an LED lamp with total power of 9W, comprising 6 lamp beads with 365nm wavelength and 4 lamp beads with 395nm wavelength. The purity of the nitrogen is 99.995%, and the water absorption rate of the resin is measured by referring to the method of GB/T22905-2008 paper diaper high absorbent resin.
In a preferred embodiment, a chain transfer agent for free radical polymerization is added to the wastewater containing the multifunctional acrylate to control the degree of crosslinking and the morphology of the polymer resulting in molecular chains. Useful chain transfer agents include thiol compounds such as 2-mercaptoethanol, 3-mercaptopropylene glycol, 2-mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoimidazole, and carbon tetrabromide, hexabromoethane, isopropanol, and combinations thereof. The amount of chain transfer agent used, depending on the chain transfer agent used, may be in the range of 0 to 20w%. For example, the amount of mercaptan and isopropanol used as chain transfer agent varies greatly, and one skilled in the art can find suitable amounts of chain transfer agent by correlation and comparative testing. In the manner of example 4, mercaptopropionic acid was used as a chain transfer agent in an amount of 1w% based on the mass of acrylic acid and its salts as well as the monomers added in the waste water in the system.
Super absorbent resins are a class of functional materials that absorb tens to thousands of times their own weight, and typical examples are high molecular weight polyacrylamides and polyacrylates. The water absorption rate of polyacrylate super absorbent resin is affected by the acid neutralization degree, crosslinking degree, ion concentration of absorbed water and the like of the resin, different application purposes have different requirements on the water absorption rate of the super absorbent resin, and the water absorption rate of the super absorbent resin is at least higher than 30 times when the polyacrylate super absorbent resin is used as a water-retaining agent for agriculture, forestry and the like.
In the above examples 1 to 6, the polymerization effect of acrylic acid, methacrylic acid, acrylic acid salt and methacrylic acid salt in the wastewater after the light treatment of the wastewater containing (meth) acrylic acid and its derivatives or salts was good, there was almost no residue in the wastewater, and the water absorption ratio of the super absorbent resin prepared with the wastewater was all more than 30 times, and the water absorption ratio of example 3 was more than 500 times, and it was useful as a water retaining agent for agricultural planting, soil improvement, road slope management, water prevention and leakage stoppage, etc. In comparative example 7, the portion left after 8 g of the powder was dissolved in water was dried again to about 2 g, which showed that the acrylic acid and acrylic acid salt remained in the waste water more, the polymerization effect was poor, and the water absorption ratio was less than 10 times, which was not suitable as a water retaining agent for the above-mentioned applications.
The foregoing examples are illustrative of the principles and embodiments of the present invention and are merely provided to facilitate an understanding of the method for treating acrylic acid wastewater and the core ideas thereof. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (3)
1. A method for treating (meth) acrylic acid wastewater, comprising the steps of:
A. adding vinyl monomer and initiator into (methyl) acrylic acid wastewater to obtain solution; wherein the (methyl) acrylic acid wastewater contains one or more of methacrylic acid, acrylic acid, methacrylic acid salt or acrylic acid salt, and the content of the methacrylic acid, the acrylic acid, the methacrylic acid salt or the acrylic acid salt in the (methyl) acrylic acid wastewater is 1-20wt% of the wastewater; the vinyl monomers include monofunctional vinyl monomers; the addition amount of the monofunctional vinyl monomer is 10-20wt% of the wastewater dosage; the monofunctional vinyl monomer is selected from acrylic acid or vinyl sulfonate; the initiator is a combination of a photoinitiator and a thermal initiator; the photoinitiator is 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone, and the dosage of the 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is 0.08 to 2 weight percent of the quality of the wastewater; wherein the thermal initiator is selected from azo diisobutyl amidine hydrochloride;
B. introducing inert gas into the solution, irradiating the solution by using a UV lamp or an LED lamp with the emission wavelength of 280-415nm to initiate photopolymerization, automatically increasing the temperature of a reaction system by using the polymerization heat of the photopolymerization, and starting a thermal initiator to initiate polymerization of the residual monomers to obtain a gel polymer;
C. and dehydrating and drying the gel polymer to obtain the polymer.
2. The process of claim 1, wherein the oxygen content of the solution is less than 100ppm.
3. The method of claim 1, wherein the vinyl monomer further comprises a multifunctional vinyl monomer; the addition amount of the multifunctional vinyl monomer is 0-5wt% of the amount of wastewater, but is not 0; the multifunctional vinyl monomer is selected from methylene bisacrylamide, ethylene glycol diallyl ether, butanediol diallyl ether, polyglycol diallyl ether, trimethylolpropane triallyl ether or ethoxylated trimethylolpropane triallyl ether.
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