CN1840555A - Aqueous high molecular polymer, coagulated dehydrant for sludge and sludge coagulating method - Google Patents
Aqueous high molecular polymer, coagulated dehydrant for sludge and sludge coagulating method Download PDFInfo
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- CN1840555A CN1840555A CN 200610058496 CN200610058496A CN1840555A CN 1840555 A CN1840555 A CN 1840555A CN 200610058496 CN200610058496 CN 200610058496 CN 200610058496 A CN200610058496 A CN 200610058496A CN 1840555 A CN1840555 A CN 1840555A
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- Prior art keywords
- moles
- aam
- multipolymer
- ratio
- carboxylic acid
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- 239000010802 sludge Substances 0.000 title claims abstract description 40
- 230000001112 coagulating effect Effects 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title description 45
- 229920000642 polymer Polymers 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 70
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 33
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 25
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 23
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 12
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 4
- 230000015572 biosynthetic process Effects 0.000 claims description 73
- 239000003795 chemical substances by application Substances 0.000 claims description 43
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 18
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 18
- 238000005189 flocculation Methods 0.000 claims description 10
- 230000016615 flocculation Effects 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000004744 fabric Substances 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000007942 carboxylates Chemical class 0.000 abstract 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 239000000701 coagulant Substances 0.000 abstract 1
- 239000012024 dehydrating agents Substances 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 77
- 238000003786 synthesis reaction Methods 0.000 description 71
- 239000000203 mixture Substances 0.000 description 42
- 238000006116 polymerization reaction Methods 0.000 description 33
- -1 amino propyl Chemical group 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 11
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical class CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229940049920 malate Drugs 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- ICCVOKMKWYGITK-UHFFFAOYSA-N 1-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C(C)=C ICCVOKMKWYGITK-UHFFFAOYSA-N 0.000 description 3
- MVYVKSBVZFBBPL-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)NC(=O)C=C MVYVKSBVZFBBPL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- FDSAJHOMGQDJRF-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)OC(=O)C(C)=C FDSAJHOMGQDJRF-UHFFFAOYSA-N 0.000 description 2
- AZLCUQRXNSKNQR-UHFFFAOYSA-N 1-but-2-enoyloxypropane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)OC(=O)C=CC AZLCUQRXNSKNQR-UHFFFAOYSA-N 0.000 description 2
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 2
- DMSRIHVZKOZKRV-UHFFFAOYSA-N 2-methyl-1-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C(C)=C DMSRIHVZKOZKRV-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- SPLHZMALZSQELD-UHFFFAOYSA-N 1-(but-2-enoylamino)propane-1-sulfonic acid Chemical compound CC=CC(=O)NC(CC)S(=O)(=O)O SPLHZMALZSQELD-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- VOCDJQSAMZARGX-UHFFFAOYSA-N 1-ethenylpyrrolidine-2,5-dione Chemical compound C=CN1C(=O)CCC1=O VOCDJQSAMZARGX-UHFFFAOYSA-N 0.000 description 1
- CXKZIYUKNUMIBO-UHFFFAOYSA-N 1-phenylethyl prop-2-enoate Chemical compound C=CC(=O)OC(C)C1=CC=CC=C1 CXKZIYUKNUMIBO-UHFFFAOYSA-N 0.000 description 1
- XNQDKIWPZVPVQD-UHFFFAOYSA-N 2-(2-methylprop-2-enoylamino)ethanesulfonic acid Chemical compound CC(=C)C(=O)NCCS(O)(=O)=O XNQDKIWPZVPVQD-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- QCZPDNUGFVDHMP-UHFFFAOYSA-N 2-methyl-1-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound C(C(=C)C)(=O)OC(C(C)C)S(=O)(=O)O QCZPDNUGFVDHMP-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- CFZDMXAOSDDDRT-UHFFFAOYSA-N 4-ethenylmorpholine Chemical compound C=CN1CCOCC1 CFZDMXAOSDDDRT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000151 deposition Methods 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
- 230000006866 deterioration Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- RBVOJZBQNQTPRA-UHFFFAOYSA-N n-(1-phenylethyl)prop-2-enamide Chemical compound C=CC(=O)NC(C)C1=CC=CC=C1 RBVOJZBQNQTPRA-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
Abstract
The present invention provides a water-soluble polymer which can be used as a coagulating and dehydrating agent that does not corrode production facilities, does not raise concern of generating a dioxin or the like even when it is burned, and has good stripping performance for stripping a sludge cake from a filter cloth. The water-soluble polymer is prepared by copolymerization of a tertiary amine saturated carboxylate monomer and a water-soluble monomer having an [alpha], [beta]-unsaturated double bond. The tertiary amine saturated carboxylate monomer is obtained by reacting a saturated carboxylic acid having two or more carboxylic acid groups in a molecule with an N, N-dialkylaminoalkyl (meth)acrylate in an amount equivalent to the carboxylic acid groups of the saturated carboxylic acid.
Description
Technical field
The present invention relates to high molecular weight water soluble polymer, mud with condensing dewatering agent and sludge coagulating evaporation.
Background technology
Because sewage, dung are urinated or the biological treatment of various industry drainings, produced organic property mud of excess sludge, cohesion mud etc.Up to now, in the processed of these mud, people use cationic high molecular polymer separately, but in recent years, the increase of the mud generation that comes owing to the increase of following water displacement and the deterioration of sludge character, the cohesive force of existing cationic high molecular polymer is poor, so the treatment capacity of mud is limited, or the state of handling can not satisfy in the requirement from the aspects such as performance that filter cloth is peeled off of dewatered cake water ratio, the SS rate of recovery, filter cake, so press for improvement.
In order to address these problems, the various high molecular weight water soluble polymers (patent documentation 1) that have cationic cohesion dewatering agent and anionic property cohesion dewatering agent in molecule have been proposed.
To be cationic cohesion dewatering agent condense dewatering agent with anionic property to above-mentioned high molecular weight water soluble polymer carries out copolymerization and prepare.
As above-mentioned cationic cohesion dewatering agent, for example can use (methyl) vinylformic acid N, the hydrochloride of N-dialkyl aminoalkyl ester.
In addition, as above-mentioned anionic property cohesion dewatering agent, can use vinylformic acid, acrylamide etc.
But, the above-mentioned high molecular weight water soluble polymer of Shi Yonging all the time, be in the water of organic sludge etc. by this high molecular weight water soluble polymer being joined suspendible, organic sludge etc. cohesion and generate cohesion throw out as segregative of solid-liquid, but since the strength ratio of this cohesion throw out a little less than, so there is the problem of the insufficient grade of performance that sludge filter cake peels off from filter cloth.
In addition, as cationic cohesion dewatering agent, using (methyl) vinylformic acid N, under the situation of the dewatering agent of the hydrochloride of N-dialkyl aminoalkyl ester, because the strong acid of use hydrochloric acid etc. is so exist the corrosive problem and the problem that should be noted that careful operation of producing apparatus.
And then by the sludge filter cake that dehydration generates, still, using under the situation of hydrochloride as cationic cohesion dewatering agent, there is the problem of worrying to produce owing to burning two English in final major part by burning disposal.
Therefore, urgently expect a kind of high molecular weight water soluble polymer that the cohesion dewatering agent uses that can be used as, it does not corrode producing apparatus, even burn etc., also do not worry to produce two English etc. in addition, and then it is good to peel off the separability of sludge filter cake from filter cloth.
[patent documentation 1] Japanese kokai publication hei 8-71599 communique
Summary of the invention
In view of the above problems, problem of the present invention is to provide a kind of high molecular weight water soluble polymer that the cohesion dewatering agent uses that can be used as, and it does not corrode producing apparatus, even burn etc., also do not worry to produce two English etc. in addition, and then the separability of peeling off sludge filter cake from filter cloth is good.
Inventor of the present invention furthers investigate in order to solve above-mentioned problem, found that, utilizes following high molecular weight water soluble polymer can solve above-mentioned problem, thereby has finished the present invention.
Promptly, the invention provides a kind of high molecular weight water soluble polymer, it is characterized in that, be tertiary amine saturated carboxylic acid salt monomer and have α, the water-soluble monomer of β unsaturated double-bond carries out copolymerization formation, described tertiary amine saturated carboxylic acid salt monomer is to make saturated carboxylic acid and corresponding with the carboxylic acid group of this saturated carboxylic acid normal (methyl) vinylformic acid N that has 2 or its above carboxylic acid group in the molecule, and the N-dialkyl aminoalkyl ester reacts and obtains.
When forming tertiary ammonium salt, replace hydrochloric acid by using the saturated carboxylic acid that has 2 or its above carboxylic acid group in the molecule, can form and not corrode producing apparatus etc., can not produce materials such as two English when burning in addition yet.
In addition, use saturated carboxylic acid salt to be used as the counter ion of tertiary ammonium salt, can improve cohesion performance or stripping performance by replacing hydrochloride.
Further, have α by making, the water-soluble monomer of β unsaturated double-bond carries out copolymerization and improves cohesion performance, stripping performance.
The high molecular weight water soluble polymer that the present invention relates to is not owing to use the strong acid of hydrochloric acid etc., so do not corrode producing apparatus, can increase work efficiency in manufacturing processed.
In addition, through the cohesion throw out that the high molecular weight water soluble polymer that the present invention relates to was handled,, do not worry producing two English even carry out burning disposal yet.
Further, utilize the high molecular weight water soluble polymer that the present invention relates to, can improve cohesion performance, also can improve after this cohesion throw out is dewatered, the stripping performance when filter cloth is peeled off this cohesion throw out organic sludge.
Embodiment
Below, high molecular weight water soluble polymer of the present invention is described.
High molecular weight water soluble polymer of the present invention is a tertiary amine saturated carboxylic acid salt monomer with have α, and the water-soluble monomer of β unsaturated double-bond carries out that copolymerization forms.
Above-mentioned tertiary amine saturated carboxylic acid salt monomer is to make saturated carboxylic acid and corresponding with the carboxylic acid group of this saturated carboxylic acid normal (methyl) vinylformic acid N that has 2 or its above carboxylic acid group in the molecule, and the N-dialkyl aminoalkyl ester reacts and obtains.
As above-mentioned (methyl) vinylformic acid N, the N-dialkyl aminoalkyl ester, for example can list, (methyl) vinylformic acid N, the N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N, N-diethylamino propyl ester, (methyl) vinylformic acid N, N-dipropyl amino ethyl ester, (methyl) vinylformic acid N, the amino propyl ester of N-dipropyl, (methyl) vinylformic acid N-methyl, N-ethyl-amino ethyl ester, (methyl) vinylformic acid N-methyl, N-ethyl-amino propyl ester, (methyl) vinylformic acid N-methyl, N-propyl group-amino ethyl ester, (methyl) vinylformic acid N-methyl, N-propyl group-amino propyl ester, (methyl) vinylformic acid N-ethyl, N-propyl group-amino ethyl ester, (methyl) vinylformic acid N-ethyl, N-propyl group-amino propyl ester.
As above-mentioned saturated carboxylic acid,, just be not particularly limited so long as in 1 molecule, have 2 or its above carboxylic acid group's saturated carboxylic acid.
For example, as saturated carboxylic acid, the molecular weight that can list citric acid, oxysuccinic acid, tartrate, oxalic acid, hexanodioic acid, succsinic acid etc. is smaller or equal to 300 carboxylic acid.
Have a α as above-mentioned, the water-soluble monomer of β unsaturated double-bond can be enumerated non-ionic monomer, anionic property monomer.
Have α as this, the water-soluble monomer of β unsaturated double-bond, preferred intramolecularly has the monomer of functional groups such as carboxylic acid group, amide group, sulfonic group, cyano group, pyrrolidone-base, imidazolyl.
This has α, and the water-soluble monomer of β unsaturated double-bond can be with a kind or 2 kinds or mixing use more than it.
As above-mentioned non-ionic monomer, can list (methyl) acrylate derivative, (methyl) acrylamide derivative, contain the ethylenic monomer derived thing of nitrogen-atoms.
As above-mentioned (methyl) acrylate derivative, for example can list (methyl) vinylformic acid hydroxyl methyl esters, diglycol monotertiary (methyl) acrylate, single (methyl) acrylate of polyoxyethylene glycol (polymerization degree 3～50), single (methyl) acrylate of Polyglycerine (polymerization degree 1～10) etc.
As above-mentioned (methyl) acrylamide derivative, can enumerate (methyl) acrylamide, N-(methyl)-acrylamide, N-sec.-propyl-(methyl) acrylamide, N-methylol-(methyl) acrylamide etc.
As the above-mentioned ethylenic monomer derived thing that contains nitrogen-atoms, can enumerate vinyl cyanide, N-vinyl-2-Pyrrolidone, vinyl imidazole, N-vinyl-succinimide, p-aminophenyl ethene, N-vinylcarbazole, 2-vinyl pyridine, vinyl morpholine, (methyl) 2 cyanoethyl acrylate etc.
As above-mentioned anionic property monomer, can list unsaturated carboxylic acid, unsaturated sulfonic acid, (methyl) acryloyl polyoxyalkylene (carbonatoms 1～6) sulfuric ester etc.
As above-mentioned unsaturated carboxylic acid, for example can list (methyl) vinylformic acid, maleic anhydride, fumaric acid, methylene-succinic acid, vinyl benzoic acid etc.
As above-mentioned unsaturated sulfonic acid, for example can list, the aliphatics unsaturated sulfonic acid of carbonatoms 2～20, the aromatic series unsaturated sulfonic acid of carbonatoms 6～20, contain sulfonic (methyl) acrylate, contain sulfonic (methyl) acrylamide, (first generation) allyl group sulfosuccinic dialkylaminobenzoic acid (carbonatoms 1～20) ester etc.
As the aliphatics unsaturated sulfonic acid of above-mentioned carbonatoms 2～20, can list for example vinyl sulfonic acid etc.
As the aromatic series unsaturated sulfonic acid of above-mentioned carbonatoms 6～20, can list for example styrene sulfonic acid etc.
As above-mentioned sulfonic (methyl) acrylate that contains, for example can list, 2-(methyl) acryloxy ethyl sulfonic acid, 2-(methyl) acryloxy propanesulfonic acid, 3-(methyl) acryloxy propanesulfonic acid, 2-(methyl) acryloxy fourth sulfonic acid, 4-(methyl) acryloxy fourth sulfonic acid, 2-(methyl) acryloxy-2,2-dimethyl ethyl sulfonic acid, to (methyl) acryloxy toluene sulfonic acide etc.
As above-mentioned sulfonic (methyl) acrylamide that contains, can list for example 2-(methyl) acrylamido ethyl sulfonic acid, 2-(methyl) acrylamido propanesulfonic acid, 3-(methyl) acrylamido propanesulfonic acid, 2-(methyl) acrylamido fourth sulfonic acid, 4-(methyl) acrylamido fourth sulfonic acid, 2-(methyl) acrylamido-2,2-dimethyl ethyl sulfonic acid, to (methyl) acrylamido toluene sulfonic acide etc.
As (first generation) allyl group sulfosuccinic dialkylaminobenzoic acid (carbonatoms 1～20) ester, for example can list (first generation) allyl group sulfo-succinic acid methyl esters etc.
As (methyl) acryloyl polyoxyalkylene (carbonatoms 1～6) sulfuric ester, for example can list (methyl) acryloyl polyoxyethylene (ethylene oxide adduct of mole number 2～50) sulfuric ester etc.
Has a α as above-mentioned, the water-soluble monomer of β unsaturated double-bond, preferably above-mentioned (methyl) acrylamide derivative, above-mentioned unsaturated carboxylic acid, above-mentioned sulfonic (methyl) acrylate, above-mentioned sulfonic (methyl) acrylamide that contains of containing, more preferably (methyl) acrylamide, (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl sulfonic acid, 2-(methyl) acryloxy propanesulfonic acid, 3-(methyl) acryloxy propanesulfonic acid, 2-(methyl) acrylamido propanesulfonic acid, 2-(methyl) acrylamido-2,2-dimethyl ethyl sulfonic acid.
From aspects such as the easiness that obtains and prices, through these water-soluble monomers commonly used.
In the present invention, as above-mentioned (methyl) vinylformic acid N, N-dialkyl aminoalkyl ester and above-mentioned saturated carboxylic acid and above-mentionedly have a α, the preferably combination of the water-soluble monomer of β unsaturated double-bond, can list, 1) methacrylic acid N, N-dimethylamino ethyl ester and (citric acid or oxysuccinic acid) and (methyl) acrylamide, 2) methacrylic acid N, N-dimethylamino ethyl ester and (citric acid or oxysuccinic acid) and acrylamide and (methyl) vinylformic acid, 3) methacrylic acid N, N-dimethylamino ethyl ester and (citric acid or oxysuccinic acid) combination with acrylamide and 2-(methyl) acrylamido propanesulfonic acid.
In addition, high molecular weight water soluble polymer of the present invention is above-mentioned tertiary amine saturated carboxylic acid salt monomer and the above-mentioned α of having, and the water-soluble monomer of β unsaturated double-bond carries out that copolymerization forms.
Above-mentioned tertiary amine saturated carboxylic acid salt monomer when carrying out copolymerization and above-mentionedly have a α, the ratio of components of the water-soluble monomer of β unsaturated double-bond (mole %) is 99.5: 0.5～0.5: 99.5, is preferably 90: 10～10: 90.
If ratio of components (mole %) in this scope, then makes the excellent performance of organic property sludge coagulating and dehydration.In addition, have α, the water-soluble monomer of β unsaturated double-bond is under the above situation of 2 kinds or its, is 2 kinds or its above monomeric aggregate value.
As making above-mentioned tertiary amine saturated carboxylic acid salt monomer and the above-mentioned α of having, the water-soluble monomer of β unsaturated double-bond carries out the method for copolymerization, can be undertaken by present known thermopolymerization or photopolymerization, be not particularly limited, but preference illustrates the situation of carrying out copolymerization with this light polymerization process below as carrying out with the light polymerization process of putting down in writing in the special fair 8-5926 communique of Japan.
Tertiary amine saturated carboxylic acid salt monomer with have α, the copolymerization of the water-soluble monomer of β unsaturated double-bond is to be undertaken by the solution polymerization in the aqueous solution.
Under the situation of solution polymerization, in this tertiary amine saturated carboxylic acid salt monomer, cooperate to have α the water-soluble monomer of β unsaturated double-bond and the strength of solution that obtains is general preferred in the scope of 65～80 weight %.
Have α when cooperating in this tertiary amine saturated carboxylic acid salt monomer, the concentration of the water-soluble monomer of β unsaturated double-bond and the solution that obtains is during less than 65 weight %, the problem that exists production efficiency to reduce.
In addition, have α if cooperate in this tertiary amine saturated carboxylic acid salt monomer, the water-soluble monomer of β unsaturated double-bond and the strength of solution that obtains surpasses 80 weight % then exists to be difficult to the problem that controlled polymerization heat release, product property descend.
Polymerization starter when carrying out photopolymerization can use for example initiator of benzophenone, bitter almond oil camphor, benzoin alkylether etc.
The usage quantity of this polymerization starter, with respect to the above-mentioned tertiary amine saturated carboxylic acid salt monomer of 100 weight parts with above-mentionedly have a α, the mixture of the water-soluble monomer of β unsaturated double-bond is preferably 0.001～1.0 weight part.
Be used to cause the device of photopolymerisable luminous energy as generation, usually, can use commercially available, obtainable xenon lamp, tungsten lamp, halogen lamp, carbon arc lamp, in addition, as mercuryvapour lamp, also can use high pressure mercury vapour lamp, Cooper-Hewitt lamp, extra-high-pressure mercury vapour lamp, but generally use high pressure mercury vapour lamp.
The wavelength that uses has certain difference along with the difference of the kind of the Photoepolymerizationinitiater initiater that uses, and is the most effective in the scope of 300～380nm usually.
As this polymerization process, be to make the tertiary amine saturated carboxylic acid salt monomer of normal solution concentration and have α, the mixing solutions of the water-soluble monomer of β unsaturated double-bond is behind the adding Photoepolymerizationinitiater initiater, enclose the rare gas element of nitrogen or carbonic acid gas etc., remove the molten oxygen of depositing.
If with the above-mentioned mixing solutions of ultra violet lamp, then polymerization is carried out at short notice, can obtain the target high molecular weight water soluble polymer.
High molecular weight water soluble polymer of the present invention can be used as mud with condensing dewatering agent.Under as the situation of mud, need have the molecular weight of proper range with the cohesion dewatering agent.
In the field of mud, often use the numerical value of so-called limiting viscosity to come the molecular weight of mark proper range with the cohesion dewatering agent.
In high molecular weight water soluble polymer of the present invention, limiting viscosity is 3dl/g or more than it.
In order to make limiting viscosity is 3dl/g or more than it, can by tertiary amine saturated carboxylic acid salt monomer with have α, use chain-transfer agent to adjust when the water-soluble monomer of β unsaturated double-bond carries out copolymerization.As this chain-transfer agent, can use the alcohols of Virahol, vinyl carbinol etc., the phosphorous acid salt of the thio-alcohol of Thiovanic acid, thioglycerol etc., sodium hypophosphite etc.
When limiting viscosity during less than 3dl/g, worry that the cohesive force of organic sludge etc. dies down, the cohesion throw out diminishes, and dewatering reduces.
In addition, limiting viscosity is measured according to the method for embodiment record.
Above-mentioned mud is with condensing the usage quantity of dewatering agent with respect to organic sludge, under 2.5 weight part organic sludges (absolute dry condition) are suspended in situation in 100 weight parts waters, this mud is 0.002～0.1 weight part with the cohesion dewatering agent, is preferably 0.003～0.075 weight part.
When this mud was used the cohesion dewatering agent less than 0.002 weight part, worry can not form the cohesion throw out, can not carry out solid-liquid separation.
In addition, when this mud is used the cohesion dewatering agent greater than 0.1 weight part, worry to occur toughness, make the cohesion throw out be difficult to carry out solid-liquid separation, dehydration.
Here, above-mentioned so-called absolute dry condition is meant moisture free state in the organic sludge.
Above-mentioned mud is being made an addition to the cohesion dewatering agent under the situation about using in the organic sludge, and as required, can merge use inorganic is flocculation agent.
As merging use inorganic is flocculation agent, has no particular limits, and for example can list polymerization iron (polyiron sulfate), Tai-Ace S 150, poly aluminium chloride, iron(ic) chloride, ferrous sulfate etc.Merge using inorganic is under the situation of flocculation agent, preferably in organic sludge, add inorganic is flocculation agent and stir after, add this mud with the cohesion dewatering agent.
Merge to use above-mentioned mud with condensing dewatering agent and above-mentioned inorganic when being flocculation agent, this is inorganic to be the usage quantity of flocculation agent, and with respect to the organic sludge of 100 weight parts, this is inorganic to be that flocculation agent is 0.01～0.5 weight part, is preferably 0.03～0.3 weight part.
Merge to use above-mentioned mud with the cohesion dewatering agent and above-mentioned inorganic be in the sludge coagulating dewatering of flocculation agent, when inorganic be the usage quantity of flocculation agent during less than 0.01 weight part, worry not have and above-mentioned mud with the merging result of use of condensing dewatering agent.
In addition, under situation about using with the cohesion dewatering agent, also can add the acidic substance of thionamic acid, sodium pyrosulfate etc. as mud.Adding these acidic substance is to be used for making the alkaline components of this mud with cohesion dewatering agent dissolved dissolving water in order to neutralize.The usage quantity of these acidic substance can be according to kind (for example trade effluent, Urban water supply, the sewage disposal water etc.) adjustment that suit of used water of when dissolving.
Condensing method as utilizing above-mentioned mud with the cohesion dewatering agent for example can list, and this mud is made an addition in the organic sludge with the cohesion dewatering agent, mixes and stirs, and forms and condenses throw out, makes this cohesion throw out dehydration method with water extracter then.
This dehydration utilizes gravity thickener, pressure dewatering machine and centrifuge to carry out usually.
As above-mentioned gravity thickener, can list rotating screen etc.
As above-mentioned pressure dewatering machine, can list belt press, screw press, caterpillar roller press, filter press etc.
In addition, as centrifuge, can list screw rod decanting vessel, basket type decanting vessel etc.
As preferred water extracter wherein, can list pressure zone water extracter, screw rod squeezing centrifuge etc.
Use the organic sludge of above-mentioned mud as becoming, can list the mixing sludge of the raw sludge of for example sewage dung urine, industrial water drainage etc., the mud that produces by microbiological treatment (excess sludge, digested sludge) and these mud etc. with the object of cohesion dewatering agent.
Embodiment
Specify the present invention below by embodiment, but the present invention is not subjected to any qualification of these embodiment.
In addition, in the following embodiments, with methacrylic acid N, N-dimethylamino ethyl ester tertiary amine Citrate trianion note is done the DM Citrate trianion, with methacrylic acid N, N-dimethylamino ethyl ester tertiary amine malate is designated as the DM malate, with methacrylic acid N, N-dimethylamino ethyl ester Amine from Tertiary Amine Hydrochloride is designated as the DM hydrochloride, with methacrylic acid N, N-diethylamino ethyl ester tertiary amine Citrate trianion is designated as the DE Citrate trianion, with methacrylic acid N, N-diethylamino ethyl ester tertiary amine malate is designated as the DE malate, with methacrylic acid N, N-diethylamino ethyl ester Amine from Tertiary Amine Hydrochloride is designated as the DE hydrochloride, and acrylamide is designated as AAm, vinylformic acid is designated as AAc, 2-acrylamido propanesulfonic acid is designated as ATBS.
(measuring method of ir spectrophotometry)
Use BIO-RAD society system, the machine class title: FTS-135 measures.
Fluid composition is clamped with the KBr crystallization plates and is measured, and solid-like composition is pulverized mixing with the KBr powder, carries out tableted with the tablet former, measures.
(measuring method of throw out diameter)
By estimating the diameter of measuring the cohesion throw out, described cohesion throw out is to add mud with the cohesion dewatering agent in organic sludge, and stirs and generate.
(measuring method of the water ratio of sludge filter cake)
Measure the weight of the sludge filter cake after just squeezing, this sludge filter cake is put into 105 ℃ drying machine, remove moisture.When dried weight reached constant, gravimetry was obtained water ratio.
(assay method of transparency)
Use diaphanometer to measure the clarification of filtrate.In diaphanometer, add sample, measure the height of the water layer in the time of can seeing the two-wire of the marking plate that is positioned over the bottom clearly by water layer.
(measuring method of limiting viscosity)
1) adjustment of test sample solution
About 0.2g sample (high molecular weight water soluble polymer) is weighed in the 200ml tool plug Erlenmeyer flask, adds pure water and make the evaporation of residual composition be scaled 0.2%, and make its dissolving, use magnetic stirring apparatus to stir 1 hour with 300rpm, and airtight.After this solution being placed a night (about 15～24 hours), stirred 1 hour with 300rpm with magnetic stirring apparatus.
Use glass filter (3G-1) that this aqueous solution of 0.2% is slowly filtered, remove insoluble composition.
One division transfer pipet with 25ml is taken to this filtrate in the 100ml tool plug Erlenmeyer flask, adds the sodium nitrate solution of the 2N of 25ml with the one division transfer pipet.Formed the sodium nitrate solution of 0.1% 1N like this.
As mother liquor, the sodium nitrate solution that uses 1N adjusts 0.08%, 0.06%, 0.04%, 0.02% sample solution as diluent in 100ml tool plug Erlenmeyer flask with the sodium nitrate solution of this 1N of 0.1%.
2) preparation of viscometer (Kan Nong-Fen Sike type)
Use vent fan, viscometer is cleaned 5 times or more than it, flow through acetone, drying (10 minutes or more than it) is carried out in inside with pure water.
3) mensuration of the blank value of viscometer
Kan Nong-Fen Sike type viscometer vertically is placed in the thermostatic bath that is adjusted to 30 ± 0.1 ℃ in advance, to the sodium nitrate solution that wherein adds 10ml 1N, places and measure after 20～30 minutes with the one division transfer pipet.After using rubber pipette bulb (gum spoit) that liquid level is risen to the position of the 10～15mm that is higher than above-mentioned viscometer graticule during mensuration, make under the liquid spontaneous current, measure liquid level by the time between the graticule about this viscometer.Repeat this operation 2 times or more than it, continue to measure until the difference of measured value in 0.2 second or its.With the blank value (T0) of its mean value as viscometer.
4) mensuration of viscosity
By with above-mentioned 3) same operation, adding the 10ml sample concentration with the one division transfer pipet in viscometer is each sample solution of 0.08%, 0.06%, 0.04%, 0.02%, measures the time that flows down.
5) calculating of limiting viscosity
As X-axis, as Y-axis, calculate orthoscopic with reduced viscosity, the Y value when obtaining X=0 with the concentration of sample solution with method of least squares.Should be worth as limiting viscosity.
The calculating of reduced viscosity is to obtain according to the formula of η sp/C=(η rel-1)/C.Here, η rel=T/T0, η sp=η rel-1, T: the time that flows down (second) of sample solution, T0: the time that flows down (second) of blank solution, η rel: relative viscosity, η sp: specific viscosity, C: the concentration of sample solution (%), η sp/C: reduced viscosity (dl/g).
(synthesis example 1)
In the 279.5g deionized water, add 520.6g (3.316mol) methacrylic acid N successively, N-dimethylamino ethyl ester, 212.2g (1.105mol) citric acid, 26.1g (0.368mol) acrylamide, 1.52g thiocarbamide, 0.076g polyoxyalkylene alkyl (the HLB value is about 11), 0.049g sodium hypophosphite, and stir, (ratio of components is 90 moles of %: 10 moles of %) to have synthesized solid component concentration and be 73.0% DM Citrate trianion monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 2)
Use the method the same with synthesis example 1, (ratio of components is 40 moles of %: 60 moles of %) to have synthesized solid component concentration and be 70.0% DM Citrate trianion monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 3)
Use the method the same with synthesis example 1, (ratio of components is 10 moles of %: 90 moles of %) to have synthesized solid component concentration and be 65.0% DM Citrate trianion monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 4)
Use the method the same with synthesis example 1, (ratio of components is 30 moles of %: 60 moles of %: 10 moles of %) to have synthesized solid component concentration and be 65.0% DM Citrate trianion monomer and the mixture of AAm and AAc.The usage quantity of raw material has been shown in the table 1.
(synthesis example 5)
Use the method the same with synthesis example 1, (ratio of components is 25 moles of %: 45 moles of %: 30 moles of %) to have synthesized solid component concentration and be 65.0% DM Citrate trianion monomer and the mixture of AAm and AAc.The usage quantity of raw material has been shown in the table 1.
(synthesis example 6)
Use the method the same with synthesis example 1, (ratio of components is 35 moles of %: 60 moles of %: 5 moles of %) to have synthesized solid component concentration and be 65.0% DM Citrate trianion monomer and the mixture of AAm and ATBS.The usage quantity of raw material has been shown in the table 1.
(synthesis example 7)
Use the method the same with synthesis example 1, (ratio of components is 40 moles of %: 60 moles of %) to have synthesized solid component concentration and be 70.0% DM malate monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 8)
Use the method the same with synthesis example 1, (ratio of components is 40 moles of %: 60 moles of %) to have synthesized solid component concentration and be 67.0% DM hydrochloride monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 9)
Use the method the same with synthesis example 1, (ratio of components is 30 moles of %: 60 moles of %: 10 moles of %) to have synthesized solid component concentration and be 67.0% DM hydrochloride monomer and the mixture of AAm and AAc.The usage quantity of raw material has been shown in the table 1.
(synthesis example 10)
Use the method the same with synthesis example 1, (ratio of components is 90 moles of %: 10 moles of %) to have synthesized solid component concentration and be 73.0% DE Citrate trianion monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 11)
Use the method the same with synthesis example 1, (ratio of components is 40 moles of %: 60 moles of %) to have synthesized solid component concentration and be 70.0% DE Citrate trianion monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 12)
Use the method the same with synthesis example 1, (ratio of components is 10 moles of %: 90 moles of %) to have synthesized solid component concentration and be 65.0% DE Citrate trianion monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 13)
Use the method the same with synthesis example 1, (ratio of components is 30 moles of %: 60 moles of %: 10 moles of %) to have synthesized solid component concentration and be 65.0% DE Citrate trianion monomer and the mixture of AAm and AAc.The usage quantity of raw material has been shown in the table 1.
(synthesis example 14)
Use the method the same with synthesis example 1, (ratio of components is 25 moles of %: 45 moles of %: 30 moles of %) to have synthesized solid component concentration and be 65.0% DE Citrate trianion monomer and the mixture of AAm and AAc.The usage quantity of raw material has been shown in the table 1.
(synthesis example 15)
Use the method the same with synthesis example 1, (ratio of components is 35 moles of %: 60 moles of %: 5 moles of %) to have synthesized solid component concentration and be 65.0% DE Citrate trianion monomer and the mixture of AAm and ATBS.The usage quantity of raw material has been shown in the table 1.
(synthesis example 16)
Use the method the same with synthesis example 1, (ratio of components is 40 moles of %: 60 moles of %) to have synthesized solid component concentration and be 70.0% DE malate monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 17)
Use the method the same with synthesis example 1, (ratio of components is 40 moles of %: 60 moles of %) to have synthesized solid component concentration and be 67.0% DE hydrochloride monomer and the mixture of AAm.The usage quantity of raw material has been shown in the table 1.
(synthesis example 18)
Use the method the same with synthesis example 1, (ratio of components is 30 moles of %: 60 moles of %: 10 moles of %) to have synthesized solid component concentration and be 67.0% DE hydrochloride monomer and the mixture of AAm and AAc.The usage quantity of raw material has been shown in the table 1.
[table 1]
| Synthesis example 1 | Synthesis example 2 | Synthesis example 3 | Synthesis example 4 | Synthesis example 5 | Synthesis example 6 | Synthesis example 7 | Synthesis example 8 | Synthesis example 9 | |
| Dimethylaminoethyl methacrylate | 520.6g (3.316mol) | 349.0g (2.223mol) | 114.0g (0.726mol) | 274.3g (1.747mol) | 243.8g (1.553mol) | 285.0g (1.815mol) | 346.3g (2.206mol) | 364.7g (2.323mol) | 304.3g (1.938mol) |
| Citric acid | 212.2g (1.105mol) | 142.3g (0.741mol) | 46.5g (0.242mol) | 111.8g (0.582mol) | 99.5g (0.518mol) | 116.2g (0.605mol) | - | - | - |
| Oxysuccinic acid | - | - | - | - | - | - | 148.0g (1.104mol) | - | - |
| Hydrochloric acid (35% solution) | - | - | - | - | - | - | 242.3g (2.323mol) | 202.1g (1.938mol) | |
| Acrylamide | 26.1g (0.368mol) | 236.7g (3.334mol) | 464.0g (6.535mol) | 248.0g (3.493mol) | 198.4g (2.794mol) | 220.8g (3.110mol) | 235.0g (3.310mol) | 247.4g (3.485mol) | 275.3g (3.877mol) |
| Vinylformic acid | - | - | - | 42.0g (0.583mol) | 134.2g (1.864mol) | - | - | - | 46.5g (0.646mol) |
| 2-acrylamido propanesulfonic acid | - | - | - | - | - | 53.7g (0.259mol) | - | - | - |
| Thiocarbamide (g) | 1.52 | 1.46 | 1.35 | 1.35 | 1.35 | 1.35 | 1.46 | 1.39 | 1.39 |
| Polyoxyalkylene alkyl (* 1) (g) | 0.076 | 0.073 | 0.068 | 0.068 | 0.068 | 0.068 | 0.073 | 0.070 | 0.070 |
| Sodium hypophosphite (g) | 0.049 | 0.047 | 0.044 | 0.044 | 0.044 | 0.044 | 0.047 | 0.045 | 0.045 |
| Deionized water (g) | 279.5 | 310.4 | 362.5 | 362.4 | 362.6 | 362.8 | 309.1 | 184.1 | 210.3 |
| Add up to | 1040.0 | 1040.0 | 1040.0 | 1040. 0 | 1040.0 | 1040.0 | 1040.0 | 1040.0 | 1040.0 |
| Solid components and concentration (%) (* 2) | 73.0 | 70.0 | 65.0 | 65.0 | 65.0 | 65.0 | 70.0 | 67.0 | 67.0 |
| Synthesis example 10 | Synthesis example 11 | Synthesis example 12 | Synthesis example 13 | Synthesis example 14 | Synthesis example 15 | Synthesis example 16 | Synthesis example 17 | Synthesis example 18 | |
| Diethyl aminoethyl methacrylate | 546.7g (2.955mol) | 378.8 (2.048mol) | 140.8g (0.761mol) | 300.6g (1.625mol) | 270.1g (1.460mol) | 312.4g (1.689mol) | 375.6g (2.030mol) | 393.0g (2.124mol) | 332.7g (1.798mol) |
| Citric acid | 189.1g (0.985mol) | 131.1g (0.683mol) | 48.8g (0.254mol) | 104.1g (0.542mol) | 93.3g (0.486mol) | 108.1g (0.563mol) | - | - | - |
| Oxysuccinic acid | - | - | - | - | - | - | 136.1g (1.015mol) | - | - |
| Hydrochloric acid (35% solution) | - | - | - | - | - | - | - | 221.5g (2.124mol) | 187.5g 1.798mol |
| Acrylamide | 23.3g (0.328mol) | 218.1g (3.072mol) | 486.3g (6.849mol) | 230.8g (3.251mol) | 186.5g (2.627mol) | 205.5g (2.894mol) | 216.2g (3.045mol) | 226.2g (3.186mol) | 255.3g (3.596mol) |
| Vinylformic acid | - | - | - | 39.0g (0.542mol) | 126.1g (1.751mol) | - | - | - | 43.2g (0.600mol) |
| 2-acrylamido propanesulfonic acid | - | - | - | - | - | 50.0g (0.241mol) | - | - | - |
| Thiocarbamide (g) | 1.52 | 1.46 | 1.35 | 1.35 | 1.35 | 1.35 | 1.46 | 1.39 | 1.39 |
| Polyoxyalkylene alkyl (* 1) (g) | 0.076 | 0.073 | 0.068 | 0.1 | 0.068 | 0.068 | 0.073 | 0.07 | 0.07 |
| Sodium hypophosphite (g) | 0.049 | 0.047 | 0.044 | 0.044 | 0.044 | 0.044 | 0.047 | 0.045 | 0.045 |
| Deionized water (g) | 279.3 | 310.4 | 362.6 | 364.0 | 362.5 | 362.5 | 310.5 | 197.8 | 219.8 |
| Add up to | 1040.0 | 1040.0 | 1040.0 | 1040.0 | 1040.0 | 1040.0 | 1040.0 | 1040.0 | 1040.0 |
| Solid components and concentration (%) (* 2) | 73.0 | 70.0 | 65.0 | 65.0 | 65.0 | 65.0 | 70.0 | 67.0 | 67.0 |
* 1:HLB is about 11
* the weight of the acid of 2:(monomer weight+use) ÷ adds up to
(DM Citrate trianion-AAm (90 moles of % of ratio of components: 10 moles of %) multipolymer is synthetic)
Reactive tank is that to be equipped with cooling be the quadrangle of 25cm with the length of side of chuck, and the top of this reactive tank covers with sheet glass, and this sheet glass is provided with ultraviolet lamp.Inflate in this reactive tank with rare gas element (nitrogen), the oxygen concentration in this reactive tank is adjusted to 0.2 capacity % or below it.
In the mixing solutions of 940g, import nitrogen by the DM Citrate trianion monomer of above-mentioned synthesis example 1 gained and AAm, regulate oxygen concentration in this solution to 1mg/L or below it, add and mixing 4.23g polymerization starter solution (methanol solution of 5% bitter almond oil camphor isopropyl ether), and flow in the above-mentioned reactive tank.In this reactive tank of cooling, regulate uitraviolet intensity and make that the uitraviolet intensity of reaction tank bottom is 10W/m
2, and should ultraviolet ray 60 minutes to this monomer solution prolonged exposure.The polymer gel of gained is cut into pieces behind the shape, be crushed to about 1mm,, obtain DM Citrate trianion-AAm (90 moles of % of ratio of components: multipolymer 10 moles of %) with dry 1 hour of 80 ℃ hot air dryers with pulverizer.The limiting viscosity of this multipolymer is 5.71dl/g.Inherent viscosity is shown in table 2.
(DM Citrate trianion-AAm (40 moles of % of ratio of components: 60 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 2 gained is carried out polymerization and obtains DM Citrate trianion-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %).The limiting viscosity of this multipolymer is 6.27dl/g.Inherent viscosity is shown in table 2.
The result that IR measures: confirmed 1596cm
-1(carboxylate salt), 1669cm
-1(amido linkage), 1727cm
-1The absorption of (ester bond).
(DM Citrate trianion-AAm (10 moles of % of ratio of components: 90 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 3 gained is carried out polymerization and obtains DM Citrate trianion-AAm (10 moles of % of ratio of components: multipolymer 90 moles of %).The limiting viscosity of this multipolymer is 6.35dl/g.Inherent viscosity is shown in table 2.
(DM Citrate trianion-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: 10 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 4 gained is carried out polymerization and obtains DM Citrate trianion-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %).
The limiting viscosity of this multipolymer is 5.97dl/g.Inherent viscosity is shown in table 2.
The result that IR measures: confirmed 1619cm
-1(carboxylate salt), 1665cm
-1(amido linkage), 1728cm
-1The absorption of (ester bond).
(DM Citrate trianion-AAm-AAc (25 moles of % of ratio of components: 45 moles of %: 30 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 5 gained is carried out polymerization and obtains DM Citrate trianion-AAm-AAc (25 moles of % of ratio of components: 45 moles of %: multipolymer 30 moles of %).
The limiting viscosity of this multipolymer is 5.88dl/g.Inherent viscosity is shown in table 2.
The result that IR measures: confirmed 1619cm
-1(carboxylate salt), 1665cm
-1(amido linkage), 1728cm
-1The absorption of (ester bond).
(DM Citrate trianion-AAm-ATBS (35 moles of % of ratio of components: 60 moles of %: 5 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 6 gained is carried out polymerization and obtains DM Citrate trianion-AAm-ATBS (35 moles of % of ratio of components: 60 moles of %: multipolymer 5 moles of %).
The limiting viscosity of this multipolymer is 5.86dl/g.Inherent viscosity is shown in table 2.
The result that IR measures: confirmed 1603cm
-1(carboxylate salt), 1665cm
-1(amido linkage), 1730cm
-1(ester bond), 1040cm
-1The absorption of (sulfonic acid).
(DM malate-AAm (40 moles of % of ratio of components: 60 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 7 gained is carried out polymerization and obtains DM malate-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %).The limiting viscosity of this multipolymer is 6.32dl/g.Inherent viscosity is shown in table 2.
The result that IR measures: confirmed 1598cm
-1(carboxylate salt), 1667cm
-1(amido linkage), 1728cm
-1The absorption of (ester bond).
(DM hydrochloride-AAm (40 moles of % of ratio of components: 60 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 8 gained is carried out polymerization and obtains DM hydrochloride-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %).The limiting viscosity of this multipolymer is 6.19dl/g.Inherent viscosity is shown in table 2.
(DM hydrochloride-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: 10 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 9 gained is carried out polymerization and obtains DM hydrochloride-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %).The limiting viscosity of this multipolymer is 5.94dl/g.Inherent viscosity is shown in table 2.
(DE Citrate trianion-AAm (90 moles of % of ratio of components: 10 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 10 gained is carried out polymerization and obtains DE Citrate trianion-AAm (90 moles of % of ratio of components: multipolymer 10 moles of %).The limiting viscosity of this multipolymer is 5.64dl/g.Inherent viscosity is shown in table 2.
(DE Citrate trianion-AAm (40 moles of % of ratio of components: 60 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 11 gained is carried out polymerization and obtains DE Citrate trianion-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %).The limiting viscosity of this multipolymer is 6.03dl/g.Inherent viscosity is shown in table 2.
(DE Citrate trianion-AAm (1 0 moles of % of ratio of components: 90 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 12 gained is carried out polymerization and obtains DE Citrate trianion-AAm (10 moles of % of ratio of components: multipolymer 90 moles of %).The limiting viscosity of this multipolymer is 5.94dl/g.Inherent viscosity is shown in table 2.
(DE Citrate trianion-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: 10 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 13 gained is carried out polymerization and obtains DE Citrate trianion-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %).
The limiting viscosity of this multipolymer is 5.63dl/g.Inherent viscosity is shown in table 2.
(DE Citrate trianion-AAm-AAc (25 moles of % of ratio of components: 45 moles of %: 30 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 14 gained is carried out polymerization and obtains DE Citrate trianion-AAm-AAc (25 moles of % of ratio of components: 45 moles of %: multipolymer 30 moles of %).
The limiting viscosity of this multipolymer is 5.72dl/g.Inherent viscosity is shown in table 2.
(DE Citrate trianion-AAm-ATBS (35 moles of % of ratio of components: 60 moles of %: 5 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 15 gained is carried out polymerization and obtains DE Citrate trianion-AAm-ATBS (35 moles of % of ratio of components: 60 moles of %: multipolymer 5 moles of %).
The limiting viscosity of this multipolymer is 5.55dl/g.Inherent viscosity is shown in table 2.
(DE malate-AAm (40 moles of % of ratio of components: 60 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 16 gained is carried out polymerization and obtains DE malate-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %).The limiting viscosity of this multipolymer is 5.97dl/g.Inherent viscosity is shown in table 2.
(DE hydrochloride-AAm (40 moles of % of ratio of components: 60 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 17 gained is carried out polymerization and obtains DE hydrochloride-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %).The limiting viscosity of this multipolymer is 5.86dl/g.Inherent viscosity is shown in table 2.
(DE hydrochloride-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: 10 moles of %) multipolymer is synthetic)
Adopt the synthetic the same method with above-mentioned multipolymer, the mixture of synthesis example 18 gained is carried out polymerization and obtains DE hydrochloride-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %).The limiting viscosity of this multipolymer is 5.52dl/g.Inherent viscosity is shown in table 2.
[table 2]
| Polymkeric substance | Limiting viscosity (dl/g) |
| DM Citrate trianion-AAm (90/10) | 5.71 |
| DM Citrate trianion-AAm (40/60) | 6.27 |
| DM Citrate trianion-AAm (10/90) | 6.35 |
| DM Citrate trianion-AAm-AAc (30/60/10) | 5.97 |
| DM Citrate trianion-AAm-AAc (25/45/30) | 5.88 |
| DM Citrate trianion-AAm-ATBS (35/60/5) | 5.86 |
| DM malate-AAm (40/60) | 6.32 |
| DM hydrochloride-AAm (40/60) | 6.19 |
| DM hydrochloride-AAm-AAc (30/60/10) | 5.94 |
| DE Citrate trianion-AAm (90/10) | 5.64 |
| DE Citrate trianion-AAm (40/60) | 6.03 |
| DE Citrate trianion-AAm (10/90) | 5.94 |
| DE Citrate trianion-AAm-AAc (30/60/10) | 5.63 |
| DE Citrate trianion-AAm-AAc (25/45/30) | 5.72 |
| DE Citrate trianion-AAm-ATBS (35/60/5) | 5.55 |
| DE malate-AAm (40/60) | 5.97 |
| DE hydrochloride-AAm (40/60) | 5.86 |
| DE hydrochloride-AAm-AAc (30/60/10) | 5.52 |
(sewage sludge evaluation test)
(embodiment 1)
Get 200ml mud (TS=2.3% (solid component concentration in the mud under the absolute dry condition), pH=6.5, living excess sludge mixture) in the 300ml beaker, add DM Citrate trianion-AAm (90 moles of % of ratio of components: the aqueous solution of 0.2 weight % of multipolymer 10 moles of %), and make its addition be changed to 10.0ml, 12.5ml, 15.0ml, employing possesses the stirrer of turbine blade, stirs 30 seconds with the speed of 200rpm.
After the stirring, measure the throw out diameter of the cohesion mud that is generated, then, (Japanese Off イ Le コ Application (strain) system, trade(brand)name: Lh4085, Gas permeability are 155cc/cm to the nylon system of being covered with filter cloth
2This cohesion mud of injection in the funnel (diameter is 7cm) is adopted in exerting/second), carries out natural filtration, measures the amount of filtrate after 30 seconds.
In addition, utilize diaphanometer that the clarification of the filtrate of this moment is estimated.
Cohesion mud after filtering is taken on the filter cloth that belt press uses, with 1kg/cm
2And 2kg/cm
2Respectively carry out 1 minute squeezing, estimate the separability of squeezing back sludge filter cake, measure the water ratio of this sludge filter cake from filter cloth by estimating.It the results are shown in table 3.
In addition, the water ratio of sludge filter cake is obtained according to the method for above-mentioned record.
(embodiment 2)
Use DM Citrate trianion-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 3)
Use DM Citrate trianion-AAm (10 moles of % of ratio of components: multipolymer 90 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 4)
Use DM Citrate trianion-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 5)
Use DM Citrate trianion-AAm-AAc (25 moles of % of ratio of components: 45 moles of %: multipolymer 30 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 6)
Use DM Citrate trianion-AAm-ATBS (35 moles of % of ratio of components: 60 moles of %: multipolymer 5 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 7)
Use DM malate-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 8)
Use DE Citrate trianion-AAm (90 moles of % of ratio of components: multipolymer 10 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 9)
Use DE Citrate trianion-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 10)
Use DE Citrate trianion-AAm (10 moles of % of ratio of components: multipolymer 90 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 11)
Use DE Citrate trianion-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 12)
Use DE Citrate trianion-AAm-AAc (25 moles of % of ratio of components: 45 moles of %: multipolymer 30 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 13)
Use DE Citrate trianion-AAm-ATBS (35 moles of % of ratio of components: 60 moles of %: multipolymer 5 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(embodiment 14)
Use DE malate-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(comparative example 1)
Use above-mentioned DM hydrochloride-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(comparative example 2)
Use above-mentioned DM hydrochloride-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(comparative example 3)
Use above-mentioned DE hydrochloride-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
(comparative example 4)
Use above-mentioned DE hydrochloride-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %), carry out the operation the same with embodiment 1.It the results are shown in table 3.
[table 3]
| 0.2% solution addition (ml) | The diameter of throw out (mm) | Amount of filtrate after 30 seconds (ml) | Transparency (cm) | Filter cake moisture content (%) | Separability (* 1) | |
| Embodiment 1 | 10.0 | 0.5～1 | 65 | 2.0 | 78.6 | △ |
| 12.5 | 3～5 | 113 | 4.7 | 77.6 | ○△ | |
| 15.0 | 5～7 | 131 | 6.3 | 77.2 | ○△ | |
| Embodiment 2 | 10.0 | 0.5 | 56 | 1.2 | 79.5 | △ |
| 12.5 | 1～3 | 102 | 4.0 | 78.4 | △ | |
| 15.0 | 4～6 | 119 | 5.8 | 77.7 | ○△ | |
| Embodiment 3 | 10.0 | 0.5 | 50 | 0.8 | 80.5 | × |
| 12.5 | 1～2 | 97 | 3.5 | 79.2 | △ | |
| 15.0 | 3～4 | 110 | 4.5 | 78.3 | △ | |
| Embodiment 4 | 10.0 | 0.5 | 52 | 1.0 | 80.0 | × |
| 12.5 | 1～2 | 99 | 3.7 | 79.2 | △ | |
| 15.0 | 3～4 | 111 | 4.5 | 78.6 | △ | |
| Embodiment 5 | 10.0 | 0.5 | 50 | 0.8 | 79.7 | × |
| 12.5 | 1～2 | 96 | 3.5 | 78.9 | △ | |
| 15.0 | 3～4 | 108 | 4.4 | 78.4 | △ | |
| Embodiment 6 | 10.0 | 0.5 | 48 | 0.7 | 80.2 | × |
| 12.5 | 1～2 | 97 | 3.5 | 79.4 | △ | |
| 15.0 | 3～4 | 109 | 4.3 | 78.8 | △ | |
| Embodiment 7 | 10.0 | 0.5 | 54 | 1.2 | 79.9 | × |
| 12.5 | 1～3 | 99 | 3.8 | 78.6 | △ | |
| 15.0 | 3～5 | 117 | 5.5 | 78.0 | △ | |
| Comparative example 1 | 10.0 | 0.5 | 30 | 0.3 | 88.3 | × |
| 12.5 | 1 | 42 | 0.5 | 86.5 | × | |
| 15.0 | 1～2 | 88 | 2.8 | 83.9 | × | |
| Comparative example 2 | 10.0 | 0.5 | 33 | 0.3 | 84.2 | × |
| 12.5 | 1 | 45 | 0.6 | 82.7 | × | |
| 15.0 | 1～2 | 90 | 3.0 | 81.4 | × |
[table 3 is continuous]
| 0.2% solution addition (ml) | The diameter of throw out (mm) | Amount of filtrate after 30 seconds (ml) | Transparency (cm) | Filter cake moisture content (%) | Separability (* 1) | |
| Embodiment 8 | 10.0 | 0.5～1 | 70 | 2.0 | 79.3 | △ |
| 12.5 | 2～4 | 117 | 5.0 | 78.6 | ○△ | |
| 15.0 | 4～6 | 140 | 6.7 | 77.3 | ○ | |
| Embodiment 9 | 10.0 | 0.5 | 60 | 1.5 | 80.4 | △ |
| 12.5 | 1～2 | 107 | 4.5 | 79.2 | △ | |
| 15.0 | 3～5 | 130 | 6.3 | 77.9 | ○ | |
| Embodiment 10 | 10.0 | 0.5 | 48 | 0.8 | 81.6 | × |
| 12.5 | 1～2 | 86 | 3.0 | 80.2 | △ | |
| 15.0 | 2～3 | 99 | 3.8 | 79.6 | △ | |
| Embodiment 11 | 10.0 | 0.5～1 | 52 | 1.0 | 80.0 | × |
| 12.5 | 1～3 | 96 | 3.5 | 78.8 | ○△ | |
| 15.0 | 3～5 | 110 | 4.5 | 77.4 | ○ | |
| Embodiment 12 | 10.0 | 0.5～1 | 57 | 1.5 | 79.8 | △ |
| 12.5 | 1～3 | 103 | 4.0 | 78.6 | ○△ | |
| 15.0 | 3～5 | 124 | 6.0 | 77.2 | ○ | |
| Embodiment 13 | 10.0 | 0.5 | 50 | 0.8 | 80.1 | △ |
| 12.5 | 1～3 | 95 | 3.5 | 79.0 | △ | |
| 15.0 | 3～6 | 108 | 4.5 | 77.9 | ○ | |
| Embodiment 14 | 10.0 | 0.5 | 58 | 1.3 | 79.7 | △ |
| 12.5 | 1～3 | 106 | 4.3 | 78.5 | ○△ | |
| 15.0 | 2～4 | 127 | 6.1 | 77.9 | ○ | |
| Comparative example 3 | 10.0 | 0.5～2 | 33 | 0.4 | 85.9 | × |
| 12.5 | 1～4 | 43 | 0.6 | 84.2 | × | |
| 15.0 | 3～6 | 90 | 3.0 | 82.8 | × | |
| Comparative example 4 | 10.0 | 0.5～2 | 36 | 0.5 | 84.4 | × |
| 12.5 | 1～4 | 47 | 0.8 | 82.9 | × | |
| 15.0 | 3～6 | 95 | 3.3 | 81.3 | × |
(* 1) separability evaluation
Zero: intactly peel off
Zero △: adhere to about 10%
△: adhere to about 30%
*: adhere to about 50%
(merging the sewage sludge evaluation test of using polymerization iron)
(embodiment 15)
Get 200ml mud (TS=2.3%, pH=6.5, living excess sludge mixture) in the 300ml beaker, after adding 0.1ml polymerization iron (Fe=11 weight %) and mixing, add 10.0ml DM Citrate trianion-AAm (90 moles of % of ratio of components: the aqueous solution of 0.2 weight % of multipolymer 10 moles of %), employing possesses the stirrer of turbine blade, stirs 30 seconds with the speed of 200rpm.
After the stirring, measure the throw out diameter of the cohesion mud that is generated, then, (Japanese Off イ Le コ Application (strain) system, trade(brand)name: Lh4085, Gas permeability are 155cc/cm to the nylon system of being covered with filter cloth
2This cohesion mud of injection in the funnel (diameter is 7cm) is adopted in exerting/second), carries out natural filtration, measures the amount of filtrate after 30 seconds.
In addition, utilize diaphanometer that the clarification of the filtrate of this moment is estimated.
Cohesion mud after filtering is taken on the filter cloth that belt press uses, with 1kg/cm
2And 2kg/cm
2Respectively carry out 1 minute squeezing,, measure the water ratio of this sludge filter cake by estimating the sludge filter cake estimated after the squeezing separability from filter cloth.Make the addition of above-mentioned polymerization iron be changed to 0.2ml, 0.3ml, carry out said determination.It the results are shown in table 4.
(embodiment 16)
Use DM Citrate trianion-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 17)
Use DM Citrate trianion-AAm (10 moles of % of ratio of components: multipolymer 90 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 18)
Use DM Citrate trianion-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 19)
Use DM Citrate trianion-AAm-AAc (25 moles of % of ratio of components: 45 moles of %: multipolymer 30 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 20)
Use DM Citrate trianion-AAm-ATBS (35 moles of % of ratio of components: 60 moles of %: multipolymer 5 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 21)
Use DM malate-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 22)
Use DE Citrate trianion-AAm (90 moles of % of ratio of components: multipolymer 10 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 23)
Use DE Citrate trianion-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 24)
Use DE Citrate trianion-AAm (10 moles of % of ratio of components: multipolymer 90 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 25)
Use DE Citrate trianion-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 26)
Use DE Citrate trianion-AAm-AAc (25 moles of % of ratio of components: 45 moles of %: multipolymer 30 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 27)
Use DE Citrate trianion-AAm-ATBS (35 moles of % of ratio of components: 60 moles of %: multipolymer 5 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(embodiment 28)
Use DE malate-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(comparative example 5)
Use above-mentioned DM hydrochloride-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(comparative example 6)
Use above-mentioned DM hydrochloride-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(comparative example 7)
Use above-mentioned DE hydrochloride-AAm (40 moles of % of ratio of components: multipolymer 60 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
(comparative example 8)
Use above-mentioned DE hydrochloride-AAm-AAc (30 moles of % of ratio of components: 60 moles of %: multipolymer 10 moles of %), carry out the operation the same with embodiment 15.It the results are shown in table 4.
[table 4]
| Polymerization iron addition (ml) | Throw out diameter (mm) | Amount of filtrate after 30 seconds (ml) | Transparency (cm) | Filter cake moisture content (%) | Separability (* 1) | |
| Embodiment 15 | 0.1 | 1 | 92 | 3.3 | 78.3 | △ |
| 0.2 | 2～3 | 108 | 4.3 | 77.4 | ○△ | |
| 0.3 | 3～44 | 131 | 6.3 | 76.8 | ○ | |
| Embodiment 16 | 0.1 | 0.5～1 | 79 | 2.5 | 78.7 | △ |
| 0.2 | 2 | 98 | 3.5 | 78.0 | △ | |
| 0.3 | 2～33 | 120 | 5.3 | 77.4 | ○△ | |
| Embodiment 17 | 0.1 | 1 | 65 | 1.6 | 79.2 | △ |
| 0.2 | 1～2 | 88 | 3.0 | 78.6 | △ | |
| 0.3 | 2～3 | 105 | 4.0 | 78.1 | △ | |
| Embodiment 18 | 0.1 | 1 | 84 | 3.0 | 78.7 | △ |
| 0.2 | 2～4 | 103 | 4.0 | 77.9 | ○△ | |
| 0.3 | 3～5 | 125 | 5.5 | 77.2 | ○△ | |
| Embodiment 19 | 0.1 | 1～2 | 82 | 2.5 | 78.4 | △ |
| 0.2 | 2～5 | 101 | 4.0 | 77.6 | ○△ | |
| 0.3 | 3～6 | 122 | 5.3 | 76.9 | ○ | |
| Embodiment 20 | 0.1 | 1 | 83 | 2.8 | 78.8 | △ |
| 0.2 | 2～4 | 102 | 4.0 | 77.8 | ○△ | |
| 0.3 | 3～5 | 124 | 5.4 | 77.2 | ○△ | |
| Embodiment 21 | 0.1 | 0.5～1 | 76 | 2.4 | 79.0 | △ |
| 0.2 | 1～3 | 94 | 3.3 | 78.2 | △ | |
| 0.3 | 2～3 | 115 | 5.0 | 77.5 | ○△ | |
| Comparative example 5 | 0.1 | 0.5 | 40 | 0.5 | 83.3 | × |
| 0.2 | 0.5～1 | 52 | 1.0 | 81.9 | × | |
| 0.3 | 1～2 | 91 | 2.7 | 80.4 | × | |
| Comparative example 6 | 0.1 | 1～3 | 50 | 1.0 | 81.8 | × |
| 0.2 | 2～6 | 64 | 1.5 | 80.5 | × | |
| 0.3 | 3～7 | 98 | 3.6 | 79.7 | △ |
[table 4 is continuous]
| Polymerization iron addition (ml) | Throw out diameter (mm) | Amount of filtrate after 30 seconds (ml) | Transparency (cm) | Filter cake moisture content (%) | Separability (* 1) | |
| Embodiment 22 | 0.1 | 1 | 90 | 3.3 | 78.6 | △ |
| 0.2 | 1～2 | 109 | 4.2 | 77.6 | ○△ | |
| 0.3 | 2～3 | 131 | 6.0 | 76.5 | ○ | |
| Embodiment 23 | 0.1 | 0.5～1 | 76 | 2.5 | 79.7 | △ |
| 0.2 | 1～2 | 92 | 3.3 | 78.5 | △ | |
| 0.3 | 2 | 117 | 4.8 | 77.9 | ○△ | |
| Embodiment 24 | 0.1 | 0.5～1 | 60 | 1.5 | 80.9 | × |
| 0.2 | 1 | 79 | 2.5 | 79.9 | △ | |
| 0.3 | 1～2 | 100 | 3.8 | 78.6 | △ | |
| Embodiment 25 | 0.1 | 1 | 86 | 3.0 | 78.6 | △ |
| 0.2 | 1～2 | 104 | 4.0 | 77.7 | ○△ | |
| 0.3 | 3～4 | 127 | 5.7 | 76.8 | ○ | |
| Embodiment 26 | 0.1 | 1 | 90 | 3.3 | 78.7 | △ |
| 0.2 | 1～3 | 114 | 4.5 | 77.3 | ○△ | |
| 0.3 | 3～4 | 129 | 6.0 | 76.5 | ○ | |
| Embodiment 27 | 0.1 | 1 | 88 | 3.0 | 78.9 | △ |
| 0.2 | 1～2 | 105 | 4.0 | 78.0 | ○△ | |
| 0.3 | 3～4 | 125 | 5.5 | 77.2 | ○ | |
| Embodiment 28 | 0.1 | 0.5～1 | 72 | 2.3 | 79.4 | △ |
| 0.2 | 1～2 | 93 | 3.3 | 78.3 | ○△ | |
| 0.3 | 2～3 | 114 | 4.6 | 77.6 | ○ | |
| Comparative example 7 | 0.1 | 0.5 | 31 | 0.3 | 82.3 | × |
| 0.2 | 1 | 44 | 0.6 | 80.7 | × | |
| 0.3 | 1～2 | 90 | 3.3 | 79.8 | × | |
| Comparative example 8 | 0.1 | 0.5 | 34 | 0.3 | 81.2 | × |
| 0.2 | 1 | 50 | 1.0 | 80.3 | × | |
| 0.3 | 2 | 97 | 3.5 | 79.4 | △ |
(* 1) separability evaluation
Zero: intactly peel off
Zero △: adhere to about 10%
△: adhere to about 30%
*: adhere to about 50%
In embodiment 1～28, filtrate clarification property and separability improve.
Claims (4)
1. high molecular weight water soluble polymer, it is characterized in that, be tertiary amine saturated carboxylic acid salt monomer and have α, the water-soluble monomer of β unsaturated double-bond carries out copolymerization formation, described tertiary amine saturated carboxylic acid salt monomer is to make saturated carboxylic acid and corresponding with the carboxylic acid group of this saturated carboxylic acid normal (methyl) vinylformic acid N that has 2 or its above carboxylic acid group in the molecule, and the N-dialkyl aminoalkyl ester reacts and obtains.
2. high molecular weight water soluble polymer as claimed in claim 1 is characterized in that, the ratio of components of above-mentioned tertiary amine saturated carboxylic acid salt monomer and above-mentioned water-soluble monomer (mole %) is 99.5: 0.5～0.5: 99.5.
3. a mud is characterized in that with the cohesion dewatering agent, contains claim 1 or 2 described high molecular weight water soluble polymers and forms.
4. a sludge coagulating evaporation is characterized in that, merges to use the described mud of claim 3 with condensing dewatering agent and mineral-type flocculation agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP091211/2005 | 2005-03-28 | ||
| JP2005091211A JP4008932B2 (en) | 2005-03-28 | 2005-03-28 | Water-soluble polymer, sludge coagulation dehydrating agent and sludge coagulation dehydration method |
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| CN100417674C CN100417674C (en) | 2008-09-10 |
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| WO2023029796A1 (en) * | 2021-09-06 | 2023-03-09 | 中国石油化工股份有限公司 | Polymer, tackifier and preparation method therefor, and drilling fluid |
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| WO1997018167A1 (en) * | 1995-11-14 | 1997-05-22 | Cytec Technology Corp. | High performance polymer flocculating agents |
| JP4126931B2 (en) * | 2002-02-28 | 2008-07-30 | 東亞合成株式会社 | Polymer flocculant and sludge dewatering method |
| CN1206255C (en) * | 2002-06-14 | 2005-06-15 | 湖北大学 | High-performance cation type high-molecular flocculant and preparation method thereof |
| US20040087717A1 (en) * | 2002-11-04 | 2004-05-06 | Ge Betz, Inc. | Modified polymeric flocculants with improved performance characteristics |
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| WO2023029796A1 (en) * | 2021-09-06 | 2023-03-09 | 中国石油化工股份有限公司 | Polymer, tackifier and preparation method therefor, and drilling fluid |
| GB2626096A (en) * | 2021-09-06 | 2024-07-10 | China Petroleum & Chem Corp | Polymer, tackifier and preparation method therefor, and drilling fluid |
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| Publication number | Publication date |
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| JP2006273908A (en) | 2006-10-12 |
| JP4008932B2 (en) | 2007-11-14 |
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