EP3328796A1 - Organosilicon material for the decontamination of water - Google Patents
Organosilicon material for the decontamination of waterInfo
- Publication number
- EP3328796A1 EP3328796A1 EP16754410.5A EP16754410A EP3328796A1 EP 3328796 A1 EP3328796 A1 EP 3328796A1 EP 16754410 A EP16754410 A EP 16754410A EP 3328796 A1 EP3328796 A1 EP 3328796A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- halide
- propyl
- group
- trialkoxysilyl
- tris
- 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.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 163
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 30
- 238000005202 decontamination Methods 0.000 title description 2
- 230000003588 decontaminative effect Effects 0.000 title description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 18
- 125000000129 anionic group Chemical group 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000975 dye Substances 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 10
- 125000006189 4-phenyl benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims abstract description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 6
- 239000011707 mineral Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 75
- 238000001179 sorption measurement Methods 0.000 claims description 67
- 239000002243 precursor Substances 0.000 claims description 63
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims description 52
- 150000004820 halides Chemical class 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 33
- -1 methylammonium halide Chemical class 0.000 claims description 28
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 25
- 239000007983 Tris buffer Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 230000003068 static effect Effects 0.000 claims description 15
- 238000009833 condensation Methods 0.000 claims description 13
- 230000014759 maintenance of location Effects 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011324 bead Substances 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 239000003344 environmental pollutant Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 231100000719 pollutant Toxicity 0.000 claims description 8
- 229940113720 aminosalicylate Drugs 0.000 claims description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 7
- 229940012189 methyl orange Drugs 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 6
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 claims description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical group NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 claims description 4
- NFVCHSUWXAFYLS-UHFFFAOYSA-M [Cl-].CO[Si](CCC[N+](CC1=CC=CC=C1)(CCC[Si](OC)(OC)OC)CCC[Si](OC)(OC)OC)(OC)OC Chemical compound [Cl-].CO[Si](CCC[N+](CC1=CC=CC=C1)(CCC[Si](OC)(OC)OC)CCC[Si](OC)(OC)OC)(OC)OC NFVCHSUWXAFYLS-UHFFFAOYSA-M 0.000 claims description 4
- 235000012730 carminic acid Nutrition 0.000 claims description 4
- 239000004106 carminic acid Substances 0.000 claims description 4
- CGIGDMFJXJATDK-UHFFFAOYSA-N indomethacin Chemical compound CC1=C(CC(O)=O)C2=CC(OC)=CC=C2N1C(=O)C1=CC=C(Cl)C=C1 CGIGDMFJXJATDK-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 239000003295 industrial effluent Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 230000008520 organization Effects 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 claims description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 2
- MPVDXIMFBOLMNW-ISLYRVAYSA-N 7-hydroxy-8-[(E)-phenyldiazenyl]naphthalene-1,3-disulfonic acid Chemical compound OC1=CC=C2C=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1\N=N\C1=CC=CC=C1 MPVDXIMFBOLMNW-ISLYRVAYSA-N 0.000 claims description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 2
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 2
- LIKZXCROQGHXTI-UHFFFAOYSA-M acid blue 25 Chemical compound [Na+].C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S([O-])(=O)=O)C=C1NC1=CC=CC=C1 LIKZXCROQGHXTI-UHFFFAOYSA-M 0.000 claims description 2
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229940000489 arsenate Drugs 0.000 claims description 2
- FPPNZSSZRUTDAP-UWFZAAFLSA-N carbenicillin Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)C(C(O)=O)C1=CC=CC=C1 FPPNZSSZRUTDAP-UWFZAAFLSA-N 0.000 claims description 2
- 229960003669 carbenicillin Drugs 0.000 claims description 2
- DGQLVPJVXFOQEV-NGOCYOHBSA-N carminic acid Chemical compound OC1=C2C(=O)C=3C(C)=C(C(O)=O)C(O)=CC=3C(=O)C2=C(O)C(O)=C1[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O DGQLVPJVXFOQEV-NGOCYOHBSA-N 0.000 claims description 2
- 229940114118 carminic acid Drugs 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 229940080423 cochineal Drugs 0.000 claims description 2
- 229960001259 diclofenac Drugs 0.000 claims description 2
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 claims description 2
- WSALIDVQXCHFEG-UHFFFAOYSA-L disodium;4,8-diamino-1,5-dihydroxy-9,10-dioxoanthracene-2,6-disulfonate Chemical compound [Na+].[Na+].O=C1C2=C(N)C=C(S([O-])(=O)=O)C(O)=C2C(=O)C2=C1C(O)=C(S([O-])(=O)=O)C=C2N WSALIDVQXCHFEG-UHFFFAOYSA-L 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001680 ibuprofen Drugs 0.000 claims description 2
- 229960000905 indomethacin Drugs 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- PEDJBFGFRJLMJH-UHFFFAOYSA-N methyl(3-trimethoxysilylpropyl)azanium iodide Chemical compound [I-].CO[Si](CCC[NH2+]C)(OC)OC PEDJBFGFRJLMJH-UHFFFAOYSA-N 0.000 claims description 2
- UYMHPSXBRBNKOG-UHFFFAOYSA-M methyl-tris(3-trimethoxysilylpropyl)azanium iodide Chemical compound [I-].CO[Si](CCC[N+](C)(CCC[Si](OC)(OC)OC)CCC[Si](OC)(OC)OC)(OC)OC UYMHPSXBRBNKOG-UHFFFAOYSA-M 0.000 claims description 2
- 229960000698 nateglinide Drugs 0.000 claims description 2
- OELFLUMRDSZNSF-BRWVUGGUSA-N nateglinide Chemical compound C1C[C@@H](C(C)C)CC[C@@H]1C(=O)N[C@@H](C(O)=O)CC1=CC=CC=C1 OELFLUMRDSZNSF-BRWVUGGUSA-N 0.000 claims description 2
- 229940056360 penicillin g Drugs 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- FZMKKCQHDROFNI-UHFFFAOYSA-N sulfometuron Chemical compound CC1=CC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(O)=O)=N1 FZMKKCQHDROFNI-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims 2
- KHLWLJFRUQJJKQ-UHFFFAOYSA-N 3-trimethoxysilyl-n,n-bis(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(CCC[Si](OC)(OC)OC)CCC[Si](OC)(OC)OC KHLWLJFRUQJJKQ-UHFFFAOYSA-N 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 claims 1
- 125000005496 phosphonium group Chemical group 0.000 claims 1
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 abstract description 8
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 abstract description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 43
- 239000004094 surface-active agent Substances 0.000 description 31
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 19
- 238000001914 filtration Methods 0.000 description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 239000012429 reaction media Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000011088 calibration curve Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 4
- 229920001983 poloxamer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- OWFJMIVZYSDULZ-PXOLEDIWSA-N (4s,4ar,5s,5ar,6s,12ar)-4-(dimethylamino)-1,5,6,10,11,12a-hexahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O OWFJMIVZYSDULZ-PXOLEDIWSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- 239000007995 HEPES buffer Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Definitions
- the present invention relates to the field of water depollution and in particular the sorption of radionuclides or anionic species, such as inorganic anions, anionic molecular entities and negatively charged dyes or active principles.
- the present invention is of interest in the treatment of water, in particular the treatment of industrial effluents or from nuclear applications in order to eliminate the anionic species pollutants or radionuclides.
- Ion exchange resins are conventionally used to carry out a depollution of water, in particular with a view to eliminating ionic species, and more particularly anionic species.
- poly (styrene) / poly (divinylbenzene) type resins especially Amberlite type resins (IRA96 and IRA67 or IRN 78) marketed by Rohm and Haas, are used to date.
- Amberlite type resins IRA96 and IRA67 or IRN 78
- This type of resin is appreciated because of its reversibility, thus opening the possibility of recycling both the adsorbent material and the adsorbate. It turns out that one skilled in the art is constantly looking for materials whose adsorption capacities of anionic species are increased compared to these conventional materials.
- mesoporous silicas have been functionalized in the past for this purpose, in particular with a view to modulating their physico-chemical properties and more particularly their associated adsorbent capacities.
- silica base it has already been sought to find solutions for introducing an organic component into these inorganic substrates, with a view to combining the potential of organic functional variations of organic chemistry with the advantages of the stability and robustness of inorganic substrates.
- organosilicon materials of a mixed mineral / organic nature prepared from precursors comprising at least one positively charged entity chosen from an ammonium, imidazolium, guanidinium, pyridinium or phosphonium entity proved to be effective in eliminating anionic species. or radionuclides in an aqueous medium, particularly at adsorption capacities greater than 0.5 mmol / g.
- the object of the present invention is precisely to propose the use of a porous or non-porous ionosilicon-type organosilicon material formed of bricks or repeating units, each repeating unit comprising at least one positively charged entity chosen from an ammonium entity. , imidazolium, guanidinium, pyridinium or phosphonium, and being incorporated in a silicic network by at least two silicon-carbon bonds, making it possible to respond effectively to all the needs mentioned above.
- the invention relates to the use of an organosilicon material for removing an aqueous solution from radionuclides, mineral anions, anionic molecular entities and negatively charged dyes or active ingredients, characterized in that the structure of said organosilicon material is formed of repeating units, each repeating unit comprising at least one positively charged entity selected from an ammonium, imidazolium, guanidinium, pyridinium or phosphonium entity and being incorporated into a silicic network by at least two silicon-carbon bonds.
- Figure 1 N 2 adsorption-desorption isotherm at 77K of the material prepared in Example 1. (black dots, adsorption branch, gray spots, desorption branch)
- Figure 3 X-ray diffraction of ionosilices 1, 4 and 7 prepared in Example 2.
- Figure 4 SEM and TEM images of the ionosilica materials 1 and 2 prepared in Example 2.
- Figure 5 Isolation of sorption / retention of chromate anions ionosilica material 1 as prepared in Example 2 and comparison of retention capacity with a conventional anion exchange resin.
- Figure 6 Kinetics of sorption / retention of chromate anions on the three ionosilices 1, 4 and 7 as prepared in Example 2.
- FIG. 7 curve representing the adsorption capacity with respect to the para-amino salicylate of the ionosilica materials 1 and 2 prepared in Example 2.
- Figure 9 Schematic representation of an unstructured organosilicon material.
- Figure 10 Schematic representation of a nanostructured mesoporous ionosilicon material.
- Figure 11 Schematic illustration of the surface of functionalized ionosilices (left) and hybrid ionosilices (right).
- Figure 13 SEM and TEM image of SHS / BzTrisN and SHS / StyTrisN materials prepared in Example 5.
- FIG. 14 Photograph of the monolith as prepared in Example 6 before and after extraction with supercritical CO 2 .
- FIG. 15 N 2 adsorption-desorption isotherms at 77K of the material prepared in Example 6 with supercritical CO 2 extraction (black spots, adsorption branch, gray spots, desorption branch).
- FIG. 16 N 2 adsorption-desorption isotherm at 77K of the material prepared in Example 6 on the pellets obtained by flash sintering (black spots, adsorption branch, gray spots, desorption branch)
- organosilicon material according to the invention and detailed below has also been named "ionosilice”.
- silica-based solids which contain ionic substructures, linked to the silica network by covalent bonds.
- hybrid is meant that the material which relates thereto comprises an inorganic component and an organic component.
- sicic network is meant three-dimensional network formed by Si-O-Si bonds and prepared by hydrolysis and condensation reactions from alkoxysilyl groups.
- tetraalkoxysilyl precursors such as TMOS tetramethoxysilane or TEOS tetraethoxysilane
- these reactions formally lead to the formation of a Si0 2 stoichiometry network.
- organic precursors bearing trialkoxysilyl groups allows the incorporation of organic groups in the silicic network by silicon-carbon bonds, and, consequently, the formation of organosilicon materials.
- an organosilicon material according to the present invention can be carried out according to the methods described in the chapter "texture of pulverulent or porous materials" of the technical engineering manual by F. Rouquerol et al. , p 1050-1 / p 1050-24 (Texture of pulverulent or porous materials, Engineering Techniques, March 10, 2003).
- Hybrid ionosilicon material
- the hybrid ionosilicon material that can be used in the context of the present invention can be obtained by a hydrolysis / condensation process from at least one precursor and consists of substructures or bricks, also called "repetition patterns".
- Each repeating unit comprises at least one positively charged entity selected from an ammonium, imidazolium, pyridinium, guanidinium or phosphonium entity, and is incorporated into a silicic network by at least two silicon-carbon bonds.
- the synthesis by hydrolysis / condensation from at least one trisilyl cationic precursor comprising an ammonium, imidazolium, guanidinium, pyridinium or phosphonium entity, comprising at least two hydrolysable trialkoxysilyl groups gives rise to the formation of a material formed of bricks. positively charged ionic compounds which are incorporated into a silicic network by at least two silicon-carbon bonds.
- FIG. 9 Such a hybrid ionosilicon material is shown schematically in FIG. 9. It can be seen in particular that the positively charged entities are well distributed in mass in the material.
- FIG. 11 also illustrates the major structural difference between surface functionalized ionosilices (left) and hybrid ionosilices according to the present invention (right).
- the ionosilicic material according to the present invention may be in particulate form.
- the size of these particles may be between 50 nm and 5 cm, in particular between 200 nm and 2 mm, for example between 100 nm and 250 ⁇ .
- the ionosilicic material is in the form of grains, beads or monoliths, and even more particularly in the form of beads or monoliths.
- monolith means a self-supporting macroscopic object of variable shape and size according to the synthesis conditions.
- Monoliths or beads can be obtained by different routes.
- the monoliths or the beads can be obtained by shaping on the powders by means of sintering or flash sintering also called SPS. This route of preparation is illustrated in Example 6.
- the monoliths or the beads can be obtained directly by sol-gel in the solvent phase, by synthesis in multiphasic medium (Stöber method or in emulsion phase or by use of additives), or by solvent extraction in supercritical C0 2 .
- the monoliths or the beads are obtained directly by sol-gel in the solvent phase by solvent extraction in supercritical CO 2 .
- This route of preparation is illustrated in Example 6.
- the material is in the form of a powder and may have a size of between 50 nm and 50 ⁇ m, in particular between 200 nm and 5 ⁇ m, in particular between 100 nm and 1 ⁇ m.
- the material is in the form of monoliths and may have a size of between 5 mm and 5 cm.
- monoliths having a size of between 5 mm and 2 cm, in particular between 10 mm and 2 cm.
- the size of these particles may for example be measured by laser scattering, static or dynamic scattering of light, by microscopy (optical, confocal, scanning electron or transmission) according to methods well known to those skilled in the art.
- the extent of the surface of the organosilicon material is usually referred to as "area”, is usually referred to one gram of solid (specific surface or specific area or mass area [m 2 g -1 ]).
- Porosity is defined, in the context of the present invention, as the ratio of the total pore volume V p, t (corresponding to the open porosity, the closed porosity and the intergranular porosity) to the total volume apparently occupied by the solid V p, t + V s (where Vs is the volume that would be occupied by matter if it was dense, that is to say non-porous).
- the pore volume and the specific surface area can be measured by the vapor adsorption method: Measurement of surface area and porosity
- a gas adsorption-desorption isotherm is performed by measuring and plotting the curve obtained by measuring the amount of gas adsorbed on the surface of a material of known mass or volume, based on the relative pressure of gas (P / Po) and for a given temperature, with P: equilibrium pressure of the gas and P 0 : saturation vapor pressure of the gas.
- P equilibrium pressure of the gas
- P 0 saturation vapor pressure of the gas.
- the monolayer volume is determined (point B method or BET model) from this curve.
- the specific surface area can then be calculated taking into account the size of the probe molecule, for a given molecule and temperature (16.26 ⁇ for N 2 at -195.8 ° C, 14.40 ⁇ for Kr at - 195.8 ° C; 13.80 ⁇ for Ar -195.8 ° C, 10.60 or 14.80 ⁇ for H 2 0 at 20 ° C, 18.5 ⁇ for C0 2 at 20 ° C, 18, 10 ⁇ for CH 4 at-140 ° C).
- the pore volume can be calculated from the gas adsorption isotherm at the saturation level.
- the material according to the present invention may have a specific surface, especially calculated according to the method described above, of between 10 and 2000 m 2 / g, in particular between 15 and 1600 m 2 / g, and even more particularly between 20 and 1600 m 2 / g. and 1600 m 2 / g.
- the specific surface area may advantageously be between 100 and 1600 m 2 / g, in particular between 200 and 1300 m 2 /boy Wut.
- the materials that can be used in the context of the present invention can be synthesized by a "bottom-up" approach via hydrolysis / polycondensation reactions of at least one precursor comprising at least one positively charged functional group comprising at least one entity selected from an amine, imidazole, pyridine, guanidine or phosphine entity and at least two hydrolysable trialkoxysilyl groups.
- the synthesis of 'ionosilice' materials can be performed from a mixture of precursors.
- the general synthesis method below is not intended to be limiting.
- the synthesis is based on the use of at least one precursor comprising at least one entity chosen from an ammonium entity, an imidazolium entity, a guanidinium entity, a pyridinium entity and a phosphonium entity and at least two hydrolysable trialkoxysilyl groups.
- the precursor (s) can be introduced (stirring) into an aqueous solution which can then be heated, under static conditions, at a temperature of between 50 and 95 ° C., in particular between 60 and 95 ° C. 90 ° C, especially between 70 and 80 ° C, at a pH value of between 1 and 14, in particular between 1 and 12.
- the pH may be adjusted by a buffer or a strong acid, or a strong base for example selected from phosphate buffers, carbonates, HEPES, TRIS, HCl, CH 3 COOH, NaOH, KOH, NH 4 OH.
- a buffer or a strong acid for example selected from phosphate buffers, carbonates, HEPES, TRIS, HCl, CH 3 COOH, NaOH, KOH, NH 4 OH.
- the aqueous solution may further comprise an alcohol, particularly ethanol, methanol or isopropanol.
- the product obtained after heating can be recovered by filtration and air-dried, for example at a temperature ranging from 40 to 120 ° C., in particular from 60 to 100 ° C., for a period ranging from 6 to 72 hours, in particular from 12 to 24 hours.
- an additional step is preferred to obtain monoliths.
- This embodiment has the advantage of promoting the preservation of the desired properties of the material, as developed hereinafter, such as the adsorption capacity, the kinetic performance and the hydrophilicity.
- the precursors that may be used in the context of the present invention comprise at least one positively charged atom.
- This atom can be nitrogen or phosphorus.
- the precursors are chosen from cationic silyl precursors comprising at least one ammonium, imidazolium, pyridinium, guanidinium or phosphonium entity and at least two hydrolysable trialkoxysilyl groups.
- the precursor may comprise two, three or four hydrolyzable trialkoxysilyl groups.
- ionic liquids known to those skilled in the art, and most often uses nucleophilic substitution type reactions involving a base (amine, imidazole, pyridine, guanidine, phosphine ) and an alkyl halide (in: P. Wasserscheid, T. Welton (Eds.), Ionic Liquids in Synthesis, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2002, page 9-12).
- the "hydrolyzable trialkoxysilyl groups” are groups of cross-linking silane type carrying three hydrolyzable radicals chosen from alkoxy groups, in particular from (C 1 -C 3) alkoxy groups. These alkoxy groups may advantageously be chosen from methoxy, ethoxy and isopropoxy groups.
- the alkyl groups can be linear or branched and preferably are linear, a halide may be chosen from an iodide, a chloride or a bromide or a fluoride.
- a precursor may be represented by the following formula (I):
- R 1, R 2, R 3 and R 4 represent, independently of each other, a hydrogen atom, a benzyl group, a 4-phenylbenzyl group, a styrene group or a (C 1 -C 2 ) alkyl group, for example a group ( C3-Cn) alkyl, said alkyl group being optionally substituted with a trialkoxysilyl group as defined above, at least two of the groups R1, R2, R3 and R4 comprising a trialkoxysilyl group, and at most one of the groups R1, R2, R3 and R4 being a benzyl group, a 4-phenylbenzyl group or a styrene group,
- X " represents a halide
- R represents a methyl, ethyl or propyl group and in particular the methyl group or said compound may also be named tris (3 - (trialkoxysilyl) propyl) methylammonium halide.
- halide and in particular tris (3- (trimethoxysilyl) propyl) methylammonium iodide (MeTrisN), is particularly mentioned.
- MeTrisN tris (3- (trimethoxysilyl) propyl) methylammonium iodide
- R represent a methyl, ethyl or propyl group and in particular the methyl group
- said compounds possibly also being referred to as halide, and in particular tris (3- (trialkoxysilyl) propyl) ammonium and halide iodide, and in particular tetrakis iodide (3- (trialkoxysilyl) propyl) methylammonium.
- halide and in particular tris (3- (trimethoxysilyl) propyl) ammonium iodide (HTrisN) and the halide, and in particular tetrakis (3 - (trimethoxysilyl) propyl) methylammonium iodide, are especially mentioned. (TetraN).
- BzTrisN StyTrisN BiphTrisN in which R represents a methyl, ethyl or isopropyl group, and more particularly a methyl group and X " represents a halide, said compounds also being able to be named tris (3- (trialkoxysilyl) propyl) benzylammonium halide, tris halide (3- (trialkoxysilyl) propyl) - (4-styryl) ammonium and tris (3- (trialkoxysilyl) propyl) - (4-biphenyl) ammonium halide.
- halide and in particular tris (3- (trimethoxysilyl) propyl) benzylammonium chloride (BzTrisN), the halide, and in particular tris (3- (trimethoxysilyl) propyl) - chloride ( 4-styryl) ammonium (StyTrisN) and the halide, and in particular tris (3- (trimethoxysilyl) propyl) - (4-biphenyl) ammonium chloride (BiphTrisN).
- a precursor can be represented by the following formula (II):
- R1, R2, R3, R4 and R5 represent, independently of one another, a hydrogen atom, a (C1-C12) alkyl group, for example a (C3-Cn) alkyl group, optionally substituted by a trialkoxysilyl group such as defined above, at least two of the groups R1, R2, R3, R4 and R5 comprising a trialkoxysilyl group, and
- X " represents a halide
- R represents a methyl, ethyl or isopropyl group, and more particularly an ethyl group and X " represents a halide
- said compound also being capable of being named 1,3- (3- (trialkoxysilyl) propyl) -1H-imidazole halide; 3-ium.
- a precursor may be represented by the following formula (III): ( ⁇ )
- R1, R2, R3, R4, R5 and R6 represent, independently of one another, a hydrogen atom, a (C1-C12) alkyl group, for example a (C3-Cn) alkyl group, optionally substituted with a trialkoxysilyl group; as defined above, at least two of the groups R1, R2, R3, R4, R5 and R6 comprising a trialkoxysilyl group, and
- X " represents a halide
- R represents a methyl, ethyl or isopropyl group, and more particularly an ethyl group
- said compound also possibly being named N- (1,3-dimethylimidazolidin-2-ylidene) -N, N- [bis- (3) halide; (trialkoxysilyl) propyl] -1-aminium.
- halide and in particular, mention is made of the halide, and in particular N- (1,3-dimethylimidazolidin-2-ylidene) -N, N- [bis- (3 - (triethoxysilyl) -propyl] -1-aminium iodide. .
- a precursor can be represented by the following formula (IV):
- R 1, R 2, R 3, R 4, R 5 and R 6 represent, independently of one another, a hydrogen atom, a (C 1 -C 12) alkyl group, for example a (C 3 -C n) alkyl group, optionally substituted with a trialkoxysilyl group as defined above, at least two of the groups R1, R2, R3, R4, R5 and R6 comprising a trialkoxysilyl group, and
- X " represents a halide
- R represents a methyl, ethyl or isopropyl group, and more particularly an ethyl group, said compound possibly also being called 1,4 (3- (trialkoxysilyl) propyl) pyridinium halide.
- halide and in particular of 1,4 (3- (triethoxysilyl) propyl) pyridinium iodide.
- a precursor can be represented by the following formula (V):
- R 1, R 2, R 3 and R 4 represent, independently of each other, a hydrogen atom, a (C 1 -C 2 ) alkyl group, for example a (C 3 -C n) alkyl group, optionally substituted by a trialkoxysilyl group such as defined above, at least two of the groups R1, R2, R3 and R4 comprising a trialkoxysilyl group, and
- X " represents a halide.
- a precursor of formula (V) mention may be made especially of the compound of the following formula:
- R represents a methyl, ethyl or isopropyl group, and more particularly a methyl group and X " represents a halide
- said compound may also be named tetrakis halide (3- (trialkoxysilyl) propyl) phosphonium.
- TetraP tetrakis (3- (trimethoxysilyl) propyl) phosphonium halide
- TrisN tris (3- (trimethoxysilyl) propyl) ammonium iodide
- MeTrisN (trimethoxysilyl) propyl) methylammonium
- TetraN tetrakis (3- (trimethoxysilyl) propyl) ammonium iodide
- the present invention extends to the organosilicon material prepared by a hydrolysis / condensation process starting from the precursors of formula (I) defined above in which R 1, R 2, R 3 and R 4 represent, independently of the each other, a hydrogen atom, a benzyl group, a 4-phenylbenzyl group, a styrene group, a (C 1 -C 12) alkyl group, for example a (C 3 -C n) alkyl group, the said alkyl group being optionally substituted by a trialkoxysilyl group as defined above, at least two of the groups R1, R2, R3 and R4 comprising a trialkoxysilyl group, and one of the groups R1, R2, R3 and R4 being a benzyl group, a 4-phenylbenzyl group or a styrene group,
- X " represents a halide. More particularly, the present invention extends to the organosilicon material prepared by hydrolysis / condensation from one of the following three precursors:
- the material that can be used in accordance with the invention comprises pores within it.
- the material comprising such pores may have an unorganized structure.
- the material comprising such pores may have an organized structure, in particular organized periodically.
- FIG. 10 schematically illustrates this variant of the invention, namely a porous ionosilicon material, for example mesoporous, structured, for example nanostructured.
- the shape of the pores can be variable. It can be spherical, cylindrical, parallel, slit pores or bottle pores in particular.
- the term "macroporous" material means a material having an average pore size greater than 50 nm.
- mesoporous material means a material having an average pore size of between 2 and 50 nm.
- microporous material is meant a material having an average pore size of less than 2 nm.
- the term "average size" of the pores means the size defined by a median diameter of the pores D50 resulting from the pore size distribution of BJH, described hereinafter, by the adsorption or desorption branch. .
- the pore size distribution is evaluated by the BJH method (Barrett, Joyner and Halenda, Journal of the American Chemical Society 1951, 73, 373-380), which consists of stepwise analysis of nitrogen desorption isotherms at 77. K and to consider that at each step, the quantity of desorbed gas comes from cylindrical pores in which a capillary condensation of the nitrogen has occurred. The radius of these pores is obtained using Kelvin's law. The assumptions are that the pores are cylindrical and open at both ends, the wetting is perfect (the cosine of the contact angle is 1), and the condensate is in the liquid state.
- the materials are used in the form of powders, either in a sealed capillary or on a rotating plate.
- the diffractograms are recorded over a range of 0.7 to 6 ° in 2 theta (Cu Ka line) so as to target the mesopore area.
- the organosilicon material according to the invention may comprise pores with an average size of between 5 ⁇ and 5 ⁇ .
- the organosilicon material according to the invention may comprise pores with an average size of between 5 ⁇ and 2 nm.
- the organosilicon material according to the invention may comprise pores with an average size of between 2 and 50 nm.
- the organosilicon material according to the invention may comprise pores with an average size of between 50 nm and 5 ⁇ .
- the organosilicon material according to the invention comprises pores with a size of between 1 and 15 nm, and more particularly between 1.5 and 8 nm.
- the inventors have found that the adsorption properties thanks to these pores and these pore sizes are particularly interesting. In particular the adsorption capacity reaches important values and the adsorption kinetics is also very interesting.
- Pore size distribution can also influence adsorption capacity and anion exchange kinetics.
- All types of distributions are part of the invention, whether it is a monodisperse or polydisperse distribution, and whatever the pore diameter (micro-, meso- and macropreux), and whatever the shape of the pores , or more or less structured organization of the porous network.
- the inventors have found that the adsorption capacity values can be particularly high when the distribution of the pore size tends to a monodisperse distribution.
- the quality of a homogeneous or monodisperse distribution is defined by its ratio (or index) of uniformity. It is calculated from the median values, which are determined from the cumulative pore size distribution (expressed in volume or area). The median at 15% is the value of the pore diameter for which 15% of the accumulated pore volume has a size smaller than this diameter.
- the 85% median is the value of the pore diameter for which 85% of the volume of cumulative pore has a size smaller than this diameter.
- the uniformity ratio is given by the ratio of the median to 85% and the median to 15%.
- homogeneous or monodisperse pore size distribution is meant a distribution in which the uniformity ratio is less than 1.5.
- the implementation of the present invention is particularly advantageous in terms of adsorption performance when the material has a "uniform" porosity, that is to say having pores that have substantially the same size.
- the pore size is preferably monodisperse or that the pore size does not vary by more than 20% with respect to this monodispersity criterion, preferably not more than 15% and even more more preferably not more than 10%.
- the pore volume may typically be between 0 and 3 cm 3 / g.
- the pore volume may advantageously be between 0.001 and 3 cm 3 / g, more particularly between 0.002 and 3 cm 3 / g, for example between 0.002 and 2.5 cm 3 / g).
- the pore volume may advantageously be between 0.3 and 3 cm 3 / g, for example between 0.4 and 2.5 cm 3 / g.
- template molecules or “template” are used at the time of implementation of the hydrolysis / condensation process.
- surfactants are typically used in the context of the present invention. Depending on the nature of the surfactants, it is possible to target very varied pore sizes. This can lead to the different categories of materials mentioned above, namely mesoporous, macroporous or microporous materials.
- the process may consist in carrying out the polymerization of the precursor (s) in the presence of a surfactant.
- the silicate network is then formed by hydrolysis and polycondensation of the precursor (s) silicas according to the sol-gel process, around the self-assembled micelles of surfactant, which play the role of patterns (or "template”).
- template the term “master molecule” means the surfactant or set of surfactant molecules arranged together, which once removed from the material gives rise to the pores.
- the removal of the template molecules is then carried out, by extraction, according to methods well known to those skilled in the art, to lead to the desired ionosilicon material.
- organosilicon materials according to the invention can thus in particular be synthesized according to the method described in S. El Hankari et al. "Pore size control and organocatalytic properties of nano-structures, silica hybrid materials containing amino and ammonium groups", J. Mater. Chem., 2011, 21, 6948-6955.
- the synthesis is based on the use of at least one precursor as previously described by aqueous dissolution, said aqueous solution comprising the surfactant, in particular arranged in the form of micelles, as a template molecule.
- the surfactant or master molecule may be dissolved in water, optionally in the presence of a buffer, at a temperature ranging from 15 ° C. to 50 ° C., for example from 20 ° C. to 45 ° C., with stirring.
- This dissolution phase can be carried out for a duration ranging from 10 minutes to 12 hours, in particular from 30 minutes to 6 hours.
- the precursor (s) may be introduced rapidly with vigorous stirring into an aqueous solution.
- the mixture obtained can be stirred vigorously at a temperature ranging from 20 ° C to 95 ° C, for example from 30 ° C to 90 ° C, for a duration ranging from 30 minutes to 12 hours.
- the solution obtained can then be heated, under static conditions, at a temperature of between 45 ° C. and 95 ° C., in particular between 50 ° C. and 90 ° C., at a pH value of between 1 and 14, in particular between 1 and 12.
- the pH may be adjusted by a buffer, or a strong acid, or a strong base for example selected from phosphate buffers, carbonates, HEPES, TRIS, HCl, CH 3 COOH, NaOH, KOH and NH 4 OH.
- a buffer or a strong acid, or a strong base for example selected from phosphate buffers, carbonates, HEPES, TRIS, HCl, CH 3 COOH, NaOH, KOH and NH 4 OH.
- the aqueous solution may further comprise an alcohol, particularly ethanol, methanol, or isopropanol.
- the product obtained after heating can be recovered by filtration and dried in air, for example at a temperature ranging from 60 ° C. to 100 ° C., in particular from 80 ° to 90 ° C., for a period ranging from 6 to 24 hours. especially from 12 to 18 hours.
- an additional step is preferred to obtain monoliths.
- This embodiment has the advantage of promoting the preservation of the desired properties of the material, as developed hereinafter, such as the adsorption capacity, the kinetic performance and the hydrophilicity.
- the spatial arrangement of micelles is dependent on the nature of the surfactants.
- the spatial arrangement of the micelles is also dependent on the concentration of surfactants in the starting solution.
- the final structure of the material, and in particular the shape of the pores is also dependent on the concentration of anionic surfactants present in the starting solution.
- structures that can be derived from the process as described above include lamellar, 2d-hexagonal or cubic structures.
- the structuring can vary according to any physicochemical factor such as acidity, temperature or the duration of agitation.
- surfactant means an amphiphilic molecule, that is to say that it has two parts of different polarity, one lipophilic (which retains fat) and nonpolar, the other hydrophilic (miscible in water) and polar.
- anionic, cationic or nonionic surfactants among the anionic surfactants, mention may be made of carboxylate, sulphate, sulphonate and phosphate head surfactants,
- cationic surfactants examples include ammonium, imidazolium, guanidinium and pyridinium heads,
- block copolymers (diblocks, triblocks, etc.), sometimes called poloxamers for triblocks, and for example such as sold under the names Pluronics, or Synperonics, Brij, marketed by the Sigma-Aldrich, BASF and Merck, and
- anionic surfactants in particular chosen from surfactants with carboxylate heads, sulphates, sulphonates and phosphates.
- anionic surfactants with respect to surfactants of other types, causes amplification in terms of adsorption capacities.
- anionic nature of the pattern molecules creates a kind of "guide" in the orientation, the structuring of the positive charges on the surface of the pores of the material, facilitating the interaction posterior with the negatively charged entities whose elimination is targeted.
- anionic surfactants mention may in particular be made of sulphated head surfactants such as SDS (Sodium Dodecyl Sulfate) and SHS (Sodium Hexadecyl Sulfate).
- ammonium heads such as CTAB (Cetyl Trimethyl Ammonium Bromide), DTAB (Dodecyl Trimethyl Ammonium Bromide) and TTAB (Tetradecyl Trimethyl Ammonium Bromide).
- neutral surfactants such as triblock copolymers based on PEO (also known as ethylene polyoxide) and PPO (also called propylene polyoxide) groups, sold for example under the names Pluronics by the company BASF (such as eg PI 03 (EOi 7 P0 56 EOi 7 ), P84 ((EO) i 9 (PO) 4 3 (EO) i 9 ), P65 ((EO) i 9 (PO) 29 (EO) i9 ), P123 (E0 2 oP0 7 oE0 2 o) and F127 (EOiooP0 65 EOioo).
- PEO also known as ethylene polyoxide
- PPO also called propylene polyoxide
- Pluronics such as eg PI 03 (EOi 7 P0 56 EOi 7 ), P84 ((EO) i 9 (PO) 4 3 (EO) i 9 ), P65 ((EO) i 9 (PO) 29 (EO) i9 ), P123
- the content of surfactant or molecule pattern that may be present in the aqueous solution prior to the introduction of the precursor may vary from 0.1 to 10%, especially from 0.5 to 5%, in particular from 1 to 3% by weight, relative to the total weight of the aqueous solution.
- the pore size can be adjusted using any technique well known to those skilled in the art.
- blowing agents may be added to the starting solution prior to the polymerization reaction.
- the presence of such agents makes it possible to increase the pore size.
- blowing agents there may be mentioned mesitylene, toluene, xylene, trimethyl benzene, triethyl benzene, triisopropylbenzene.
- the content of swelling agent that may be present in the aqueous solution prior to the introduction of the precursor may vary from 0.1 to 50%, especially from 0.2 to 40%, in particular from 0.5 to 30% by weight, relative to the total weight of the aqueous solution.
- the organosilicon or ionosilica materials according to the invention can be used as anion exchanger or radionuclide.
- they may find utility in the treatment of water, the treatment of industrial effluents, in the retention of pollutants such as metals, polyoxanions, and / or organic molecular entities selected from dyes and active principles of drugs.
- pollutants such as metals, polyoxanions, and / or organic molecular entities selected from dyes and active principles of drugs.
- radionuclides chosen from the different forms of the following elements I, Se, Mo, Te, Cr, Sb, ...
- anionic molecular entities such as pesticides for example chosen from dichlorophenoxyacetic acid, sulfometuron ...
- the invention relates to the use of an organosilicon material for removing radionuclides from an aqueous solution, in particular as detailed above, characterized in that the structure of said organosilicon material is formed of repetition patterns, each repetition pattern comprising at least one positively charged entity and being incorporated into a silicic network by at least two silicon-carbon bonds.
- the invention relates to the use of an organosilicon material for removing an aqueous solution, mineral anions, anionic molecular entities and negatively charged dyes or active ingredients, in particular such as detailed above, characterized in that the structure of said organosilicon material is formed of repeating units, each repetition pattern being derived from a precursor comprising at least one positively charged entity and being incorporated into a silicic network by at least two silicon bonds -carbon.
- the number of silicon-carbon bonds can be two, three or four.
- materials in accordance with the invention have improved adsorption capacities with respect to conventional materials of the poly (styrene) anion exchange resin type. / poly (divinylbenzene).
- a capacity of retention was measured, reaching up to 2.5 mmol / g compared to about 1.0-1.5 mmol / g for these conventional exchangers.
- the ionosilices according to the present invention may have an adsorption capacity of between 0.5 and 4 mmol / g, in particular between 1 and 3.5 mmol / g.
- the performances of the materials are preserved when the ionosilices are used in powder form or after shaping, in particular in the form of beads or monoliths, as explained above. The preservation of these performances is particularly illustrated in example 6.
- organosilicon materials in accordance with the invention may in particular be used in aqueous solution at the whole range of conceivable concentrations of the pollutant to be eliminated, namely from weakly concentrated to highly concentrated, in other words, not only in the form of traces.
- the adsorption capacity can be measured according to the method detailed below. Method of measuring the adsorption capacity
- the volume of solution may vary from 0.5 to 500 ml, especially from 1 to 200 ml, in particular from 5 to 50 ml.
- the mass of solid may vary from 1 mg to 50 g, in particular from 1 mg to 10 g, in particular from 1 mg to 10 g.
- the initial concentration may vary from 0.001 millimol / L to 5 mol / L in particular from 0.01 millimol / L to 2 mol / L, in particular from 0.05 millimol / L to 1 mol / L.
- organosilicon or ionosilica materials according to the invention which do not exhibit pores show an adsorption capacity of interest in themselves, this is increased when pores are present in the material.
- the maximum sorption capacities are related to the quantity of exchanger groups, ie precursors initially incorporated into the material. And the accessibility of these exchange groups is also decisive with respect to the adsorption capacity, which is why the presence of pores within the material increases the adsorption capacity. For example, more than 2/3 (between 61 and 83%) of the precursors are accessible in the materials synthesized in Example 2.
- sorption kinetics it is advantageous to measure the percentage of adsorption capacity attained in 1 minute, 2 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 40 minutes, 1 hour, 80 minutes, respectively. , 120 minutes, 180 minutes, 240 minutes, 1200 minutes.
- the adsorption kinetics may be particularly rapid in the variant of the invention in which the material comprises pores. This means that because of the good accessibility of the exchange groups and the high affinity, the adsorption performance can be advantageously maintained / guaranteed, even for relatively short contact time with the effluents.
- the kinetics are considered fast when the materials have reached 90% of their maximum capacity in less than 2 hours, in particular 80% in less than 1 hour.
- the inventors have speculated that these improved performances would come from the different constitution of the materials or ionosilices according to the invention, which are composed of ionic entities, integrated into a silicic network by covalent bonds. . This difference is also at the origin of a possible higher chemical stability.
- the ionic exchange entities are thus bonded to the matrix of the material by at least two chemical bonds.
- the ionosilices according to the invention have an increased hydrophilicity.
- this property has the particular advantage of promoting faster kinetics than for conventional ion exchange resins, as illustrated in the examples.
- the hydrophilicity can be measured by adsorption of butanol in water. This measurement can be performed on a liquid flow calorimeter. The thermal effect obtained during the competitive adsorption of butanol in heptane is measured on the solid previously brought into contact with the heptane solvent. The hydrophilic surface is evaluated with respect to the amount of heat thus measured (and by comparison with a reference solid). For the hydrophobic surface, it is determined by the same procedure, by competitive adsorption of Butanol in water on the solid previously brought into contact with water. The inventors have compared the adsorption capacity values available in the literature with respect to materials obtained by co-condensation with respect to the measurements obtained for materials according to the invention.
- the materials in accordance with the invention have very good adsorption capacities and much greater than the adsorption capacities that can be obtained with materials known to those skilled in the art, obtained by means of condensation.
- the treatment of the water can be carried out on a column, with the aid of perfusing bags or else with the aid of membranes or films comprising the material according to the invention, under static shape, or in dynamic mode with continuous circulation in treatment columns.
- TetraN precursor (1.59 g) in methanol (6.7 mL) and at room temperature is added water (0.16 mL). Then, the solution is well stirred until a homogeneous mixture is formed. Then the tetrabutylammonium fluoride catalyst (TBAF) is added and the solution is stirred vigorously for 1 min. Then, a transparent gel is formed after 15 min. The gel obtained is left at room temperature for 2 days.
- TBAF tetrabutylammonium fluoride catalyst
- An organosilicon material according to the invention is obtained.
- the specific surface is 33 m 2 / g, and the adsorption-desorption isotherm of N 2 as shown in Figure 1 shows that the material has no porosity.
- the surfactant sodium hexadecyl sulfate SHS (226 mg) is dissolved in 17.9 ml of water and 2 ml of 1 M hydrochloric acid. This solution is stirred for 1 hour at 60 ° C. To this solution is then added a solution of the TrisN precursor (0.5 g) in 2 ml of ethanol. The reaction medium is stirred at 60 ° C. for 2 h and then left under static conditions at 80 ° C. for 72 h. After this time, the solution is cooled to room temperature. The material is isolated by filtration and dried at atmospheric pressure at 80 ° C for 18 h. Finally, the template is removed by repeated washing (3 times) in a solution of 200 mL ethanol / 5 mL concentrated hydrochloric acid.
- Ionosilice 2 (MeTrisN / SHS)
- the surfactant sodium hexadecyl sulfate SHS (386 mg) is dissolved in 37.0 mL of water and 2.2 mL of 1 M hydrochloric acid. This solution is stirred for 1 h at 60 ° C. To this solution is then added a solution of the MeTrisN precursor (0.7 g) in 2 ml of ethanol. The reaction medium is stirred at 60 ° C. for 2 h and then left under static conditions at 80 ° C. for 72 h. After this time, the solution is cooled to room temperature. The material is isolated by filtration and dried at atmospheric pressure at 80 ° C for 18 h. Finally, the template is removed by repeated washing (3 times) in a solution of 200 mL ethanol / 5 mL concentrated hydrochloric acid.
- Ionosilice 3 (TetraN / SHS)
- the surfactant sodium hexadecyl sulfate SHS (386 mg) is dissolved in 37.0 mL of water and 2.2 mL of 1 M hydrochloric acid. This solution is stirred for 1 h at 60 ° C. To this solution is then added a solution of TetraN precursor (1.0 g) in 1 mL of ethanol. The reaction medium is stirred at 60 ° C. for 2 hours and then left under static conditions at 80 ° C for 72 h. After this time, the solution is cooled to room temperature. The material is isolated by filtration and dried at atmospheric pressure at 80 ° C for 18 h. Finally, the template is removed by repeated washing (3 times) in a solution of 200 mL ethanol / 5 mL concentrated hydrochloric acid.
- the cetyl trimethyl ammonium bromide CTAB surfactant (362 mg) is dissolved in 23.7 ml of water and 0.5 ml of ammonia (25 wt%). This solution is stirred for 1 h at room temperature. To this solution is then added a solution of the TrisN precursor (1 g) in 2 ml of ethanol. The reaction medium is stirred at room temperature for 2 h, then left under static conditions at 80 ° C for 72 h. After this time, the solution is cooled to room temperature. The material is isolated by filtration and dried at atmospheric pressure at 80 ° C for 18 h. Finally, the template is removed by repeated washing (3 times) in a solution of 200 mL ethanol / 5 mL concentrated hydrochloric acid.
- the cetyl trimethyl ammonium bromide CTAB surfactant (362 mg) is dissolved in 23.7 ml of water and 0.5 ml of ammonia (25 wt.%). This solution is stirred for 1 h at room temperature. To this solution is then added a solution of the precursor MeTrisN (1.1 g) dissolved in 2 mL of ethanol. The reaction medium is stirred at ambient temperature for 2 h and then left under static conditions at 80 ° C. for 72 h. After this time, the solution is cooled to room temperature. The material is isolated by filtration and dried at atmospheric pressure at 80 ° C for 18 h. Finally, the template is removed by repeated washing (3 times) in a solution of 200 mL ethanol / 5 mL concentrated hydrochloric acid.
- Ionosilice 6 (TetraN / CTAB)
- the cetyl trimethyl ammonium bromide CTAB surfactant (362 mg) is dissolved in 23.7 ml of water and 0.5 ml of ammonia (25 wt.%). This solution is stirred for 1 h at room temperature. To this solution is then added a solution of TetraN precursor (1.5 g) dissolved in 2 mL of ethanol. The reaction medium is stirred at room temperature for 2 h, then left under static conditions at 80 ° C for 72 h. After this time, the solution is cooled to room temperature. The material is isolated by filtration and dried at atmospheric pressure at 80 ° C for 18 h. Finally, the template is removed by repeated washing (3 times) in a solution of 200 mL ethanol / 5 mL concentrated hydrochloric acid.
- a solution of the surfactant P123 in a water / hydrochloric acid mixture is prepared from the following quantities: 105 ml of water; 24.1 g concentrated hydrochloric acid; 4.35 g P123. This solution is stirred at 40 ° C for 3h.
- Ionosilice 8 (MeTrisN / P123)
- a solution of the surfactant P123 in a water / hydrochloric acid mixture is prepared from the following quantities: 105 ml of water; 24.1 g concentrated hydrochloric acid; 4.35 g P123. This solution is stirred at 40 ° C for 3h.
- Ionosilice 9 (TetraN / P123)
- a solution of the surfactant P123 in a water / hydrochloric acid mixture is prepared from the following quantities: 105 ml of water; 24.1 g concentrated hydrochloric acid; 4.35 g P123. This solution is stirred at 40 ° C for 3h. 4.61 g of this solution are added, at 40 ° C., 1.3 g of the MeTrisN precursor, dissolved in 1 ml of ethanol. The reaction medium is stirred at 40 ° C. for 2 h and then left under static conditions at 80 ° C. for 72 h. After this time, the solution is cooled to room temperature. The material is isolated by filtration and dried at atmospheric pressure at 80 ° C for 18 h. Finally, the template is removed by repeated washing (3 times) in a solution of 200 mL ethanol / 5 mL concentrated hydrochloric acid.
- the materials were characterized by adsorption-desorption of N 2 at 77K, X-Ray Diffraction, 13 C NMR, 29 Si NMR, IR, Scanning Electron Microscopy and Transmission.
- the specific surfaces of the porous materials range from 211 to 1019 m 2 / g.
- the overall results are given in the table below.
- the pore volumes range from 0.403 to 1.684 cm 3 / g.
- the overall results are given in Table 2 below.
- Other characterization methods confirmed the textural, structural and physicochemical properties.
- Figure 2 illustrates the isothermal adsorption-desorption curves of N 2 to 77K corresponding.
- Figure 3 illustrates the X-ray diffraction curves corresponding to the samples prepared from the TrisN precursor.
- Figure 4 shows SEM and TEM images of materials 1 and 2.
- the ionosilices as prepared in Example 2 were compared with commercial adsorbents of the exchange resin type. These are, for example, Amberlite resins (IRA96 and IRA67 for Industrial Grade Weak Base Anion Exchanger and IRN 78 for Nuclear Grade Strong Base Anion Resin).
- Amberlite resins IRA96 and IRA67 for Industrial Grade Weak Base Anion Exchanger and IRN 78 for Nuclear Grade Strong Base Anion Resin).
- a stock solution of 3 mM Cr0 4 2 ⁇ concentration is prepared. Mass m s ionosilice 10 mg is placed in a round bottom tube. A volume of ultrapure water is then added to this tube (by weighing). A volume of stock solution is then added to the same tube (by weighing). The total volume V is 20 ml, and the proportions of water and stock solution are established so as to have points distributed over the entire curve, and to cover an initial concentration range of 0.03 mM at 3 mM. The tubes are placed on a stirrer (10-15 rpm) in a thermostatically controlled chamber at 25 ° C. After stirring for 14 hours, the pH of each suspension is measured (calibration of the electrode with the buffer solutions 4- 7-10).
- the supernatant is then separated from the solid by centrifugation at 10,000 rpm for 15 minutes and then filtered (0.45 ⁇ syringe filter).
- the equilibrium concentration of each solution is measured (by ion chromatography or UV-Visible).
- a calibration curve with 4 to 6 standard solutions (between 0.06 and 0.6mM, prepared from the same stock solution) is plotted (a new curve for each new isotherm).
- the excessively concentrated spots are diluted by 10 (by weighing) in order to be compatible with the concentration range of the calibration curve.
- the material prepared without a structuring agent has a sorption capacity of 1.6 mmol / g.
- FIG. 5 represents the sorption isotherm curve of the ionosilicon material 1.
- the shape of the sorption isotherm curve shows a very high affinity from the very low concentrations of species to be retained in the solution. Note that the shape of this curve, almost vertical at very low concentrations, clearly shows the effectiveness of these materials according to the invention.
- the ion exchange resins used for comparison showed maximum capacities of 0.1; 0.05 and 1 mmol / g for IRA96, IRA67 and IR 78, respectively, for measurements carried out at free pH.
- the retention capacities of the chromate ions for the materials in accordance with the invention are in a range of 1.6 to 2.5 mmol of retained product per unit mass [g] of dry adsorbent. This result is especially interesting when compared with those obtained for conventional exchange resins, here IRN78, marketed by Rohm and Haas. 2. Exchange kinetics
- FIG. 6 illustrates the kinetics of sorption / retention of chromate anions on the three ionosilices 1, 4 and 7 as prepared in Example 2, with the following conditions, the mass of solid is de m so iid e : 10 mg and the volume in the solution is 20 ml in all cases.
- the solids are left in contact with the material for increasing periods of time, ranging from 1 minute to 20 hours.As soon as the desired contact time is reached, the supernatant is then separated from the solid and the equilibrium concentration of each solution is measured (by ion chromatography or UV-Visible).
- hydrophilic / hydrophobic character of the ionosilices as prepared in Example 2 in terms of hydrophilic / hydrophobic surface was measured by adsorption calorimetry of butanol in water or in heptane respectively (MJ Meziani, J. Zajac, DJ Jones, J. Roziere, and S.
- These materials are particularly hydrophilic compared to other structured and or functionalized materials.
- examples that may be mentioned are a non-porous hydrophilic silica (XOB015) or porous Al doped silicas, for which the values obtained are respectively 79 and 55 mJ / m 2 .
- the good hydrophilic properties are conducive to good wettability of the material, to a good accessibility of the exchanger sites. This allows increased diffusion and sorption rates, for better performance, particularly in terms of exchange kinetics, because of the very high affinity of the material for the effluent.
- Example 4 adsorption capacities with respect to organic anions
- Para-amino-salicylate can be considered as a model molecule for the anionic active principles.
- Example 2 For the para-amino salicylate sorption measurements, a protocol similar to that of Example 2 was followed.
- the solid mass m s is 5 mg
- the volume V is 20 ml.
- the concentration of the stock solution is 1 mM, for an initial concentration range of 0.01 mM to 1 mM.
- the solid is separated from the solution by centrifugation and filtration on 0.45 ⁇ syringe filter.
- the calibration curve is established for concentrations between 0.01 and 0.1 mM.
- the adsorption capacity is 1.6 mmol / g for ionosilices 1 and 2 (see FIG. 7).
- Methyl orange can be considered as a model molecule for anionic dyes.
- the solid mass m s is 2.5 mg
- the volume V is 20 ml.
- the concentration of the stock solution is 2 mM, for an initial concentration range of 0.02 mM to 2 mM.
- the solid is separated from the solution by centrifugation and filtration on 0.45 ⁇ syringe filter.
- the calibration curve is established for concentrations between 0.01 and 0.08 mM.
- the adsorption capacity is 2 and 2.5 mmol / g for ionosilices 1 and 2 (see FIG. 8).
- the benzyl chloride (1.26 g, 10 mmol) is added to a solution of tris (3- (trimethoxysily) propyl) amine (5.03 g, 10 mmol) dissolved in 10 ml of acetonitrile .
- the reaction medium was heated at 80 ° C for 48 h. after this time, the reaction medium was cooled to room temperature, and the solvent was removed under vacuum.
- the crude product was purified by repeated washing with pentane and finally isolated by vacuum drying at 50 ° C.
- the materials derived from the precursors StyTrisN and BiphTrisN were synthesized by similar protocols from 394 mg of StyTrisN or 450 mg of BiphTrisN, respectively.
- the materials were characterized by N 2 adsorption-desorption, X-ray diffraction, Scanning Electron Microscopy and Transmission. 13 C NMR, 29 Si NMR. The specific surfaces of the porous materials range from 20 to 956 m 2 / g. The overall results are given in Table 5 below. Other characterization methods confirmed the textural, structural and physicochemical properties.
- Figure 12 illustrates the corresponding N 2 -777 adsorption-desorption isotherm curves.
- Figure 13 shows SEM and TEM images of SHS / StyTrisN and SHS / BzTrisN materials.
- a monolith in the solvent phase is synthesized.
- 1 g of TrisN (1.98 mmol) is dissolved in 6 ml of ethanol (96%). The solution is stirred for 5 minutes.
- 0.02 ml of a 1M TBAF solution in THF are added.
- the solubilized monolith obtained is then poured into two closed polypropylene tubes and left for 1 day at room temperature.
- the solubilized monolith obtained is demolded so as to be immersed in an acidified ethanol solution (50 ml of ethanol with 2.5 ml of a 37% HCl solution) for 1 day.
- the monolith is dried by supercritical CO 2 using a suitable cell. The process consists in removing the ethanol present in our monolith using liquid C0 2 then supercritical without modifying the molecular structure.
- a classic cycle which has three phases.
- a first which consists in extracting the ethanol (in excess) from the cell with liquid C0 2 .
- the pressure is gradually increased from 1 bar to 63.5 bar (2 bar min -1 ) and then the pressure is left constant for 1 hour at 20 ° C.
- the second phase consists of replacing the C0 2 liquid by supercritical C0 2. for this purpose the pressure is increased to 100 bar and the temperature is increased from 20 ° C to 40 ° C (1 ° C min "1). Once these conditions are reached, the cell containing the monolith is left under supercritical CO 2 for two hours.
- the third phase is to depressurize the cell.
- This phase is carried out by decreasing the pressure from 100 bar to 1 bar with a ramp of 1 bar min- 1 while keeping the temperature at 40 ° C. Then, the temperature is decreased to room temperature.
- a cylindrical monolith of 2 cm x 0.8 cm is obtained with a mass of 0.255 g.
- a photograph of the monolith is shown in Figure 14.
- the material has a specific surface of 470 m 2 g -1, a pore volume of 1.20 cm 3 g -1 (see Figure 15). Its maximum adsorption capacity for chromates (according to the procedure described above) is 2.5 mmolg 1 .
- the ionosilicon 1 as prepared in Example 1 was shaped by flash sintering.
- the material in powder form is introduced into a specific chamber 8 mm in diameter. It is then sintered with a ramp of 50 ° C / min, from ambient to 250 ° C under nitrogen.
- the pellets thus obtained have thicknesses of between 2 mm and 4 mm.
- the material has a specific surface area of 47 m 2 g -1 , a pore volume of 0.13 cm 3 g -1 (see Fig. 16), and its maximum adsorption capacity for chromates (according to the procedure described previously in the section "Method of measurement of the adsorption capacity "in the description) is 1.8 mmol g -1 .
Abstract
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