CN107349909B - A kind of preparation method of magnetism stalk cellulose dye sorbent - Google Patents
A kind of preparation method of magnetism stalk cellulose dye sorbent Download PDFInfo
- Publication number
- CN107349909B CN107349909B CN201710598515.XA CN201710598515A CN107349909B CN 107349909 B CN107349909 B CN 107349909B CN 201710598515 A CN201710598515 A CN 201710598515A CN 107349909 B CN107349909 B CN 107349909B
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- Prior art keywords
- magnetic
- stalk
- deionized water
- dye
- added
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 60
- 239000001913 cellulose Substances 0.000 title claims abstract description 60
- 239000002594 sorbent Substances 0.000 title claims abstract description 32
- 230000005389 magnetism Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000975 dye Substances 0.000 claims abstract description 87
- 230000005291 magnetic effect Effects 0.000 claims abstract description 72
- 238000001179 sorption measurement Methods 0.000 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 20
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims abstract description 20
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 10
- 230000005415 magnetization Effects 0.000 claims abstract description 8
- 230000004043 responsiveness Effects 0.000 claims abstract description 8
- 230000005408 paramagnetism Effects 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 239000008367 deionised water Substances 0.000 claims description 63
- 229910021641 deionized water Inorganic materials 0.000 claims description 63
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 48
- 238000010792 warming Methods 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 36
- 239000010902 straw Substances 0.000 claims description 34
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- 125000002091 cationic group Chemical group 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 241000209140 Triticum Species 0.000 claims description 15
- 235000021307 Triticum Nutrition 0.000 claims description 15
- 238000000643 oven drying Methods 0.000 claims description 15
- 229920000742 Cotton Polymers 0.000 claims description 13
- 244000068988 Glycine max Species 0.000 claims description 13
- 235000010469 Glycine max Nutrition 0.000 claims description 13
- 240000008042 Zea mays Species 0.000 claims description 13
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 12
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 12
- NSDSIQGBHACTLY-UHFFFAOYSA-N Reactive Blue 5 Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S(O)(=O)=O)C=C1NC(C=1)=CC=C(S(O)(=O)=O)C=1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(O)(=O)=O)=C1 NSDSIQGBHACTLY-UHFFFAOYSA-N 0.000 claims description 11
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 11
- 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 description 11
- 235000005822 corn Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 claims description 10
- 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 9
- 229940012189 methyl orange Drugs 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
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- 239000012634 fragment Substances 0.000 claims description 7
- 239000006249 magnetic particle Substances 0.000 claims description 7
- KZMRYBLIGYQPPP-UHFFFAOYSA-O [4-[(2-chlorophenyl)-[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]methylidene]cyclohexa-2,5-dien-1-ylidene]-ethyl-[(3-sulfophenyl)methyl]azanium Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S(O)(=O)=O)C=2C(=CC=CC=2)Cl)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 KZMRYBLIGYQPPP-UHFFFAOYSA-O 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- DWCZIOOZPIDHAB-UHFFFAOYSA-L methyl green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)[N+](C)(C)C)=C1C=CC(=[N+](C)C)C=C1 DWCZIOOZPIDHAB-UHFFFAOYSA-L 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 6
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 5
- 239000010907 stover Substances 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002262 Schiff base Substances 0.000 abstract description 3
- 150000004753 Schiff bases Chemical class 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
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- 238000007254 oxidation reaction Methods 0.000 abstract description 3
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- 239000003463 adsorbent Substances 0.000 description 26
- 239000000835 fiber Substances 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 13
- 240000006394 Sorghum bicolor Species 0.000 description 12
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 12
- 235000015505 Sorghum bicolor subsp. bicolor Nutrition 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 238000003912 environmental pollution Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000009973 maize Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- -1 papermaking Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- SYZVRNJCOLTHNZ-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)N.C(C(=C)C)(=O)OCCCC Chemical compound C(C=C)(=O)O.C(C=C)(=O)N.C(C(=C)C)(=O)OCCCC SYZVRNJCOLTHNZ-UHFFFAOYSA-N 0.000 description 1
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- DPKHZNPWBDQZCN-UHFFFAOYSA-N acridine orange free base Chemical compound C1=CC(N(C)C)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 DPKHZNPWBDQZCN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229940052223 basic fuchsin Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- LGLFFNDHMLKUMI-UHFFFAOYSA-N crystal violet cation Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C1C=CC(=[N+](C)C)C=C1 LGLFFNDHMLKUMI-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- XNZQCYSOYHAYII-UHFFFAOYSA-L disodium;3-carboxy-3-hydroxypentanedioate;hydrate Chemical compound [OH-].[Na+].[Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O XNZQCYSOYHAYII-UHFFFAOYSA-L 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The present invention relates to a kind of preparation methods of magnetic stalk cellulose dye sorbent, and stalk is used to sodium chlorite and NaOH pretreatment and sodium periodate oxidation respectively, obtains aldehyde radical stalk cellulose.Magnetic nano-particle is prepared using improvement chemical coprecipitation, then it is modified that surface is carried out to it with Silane coupling agent KH550, obtain KH550 modified magnetic nanoparticle, finally by KH550 modified magnetic nanoparticle, polyethyleneimine and glutaraldehyde carry out cross-linking reaction, prepare the magnetic stalk cellulose dye sorbent with schiff bases cross-linked structure and a variety of adsorption groups, saturation magnetization is 10~30 emu/g, remanent magnetism and coercivity go to zero, with paramagnetism and magnetic responsiveness, it is 100~1000mg/L aqueous dye solutions for initial concentration, Dye Adsorption capacity reaches 50~300mg/g, 60~150min reaches adsorption equilibrium, Dye Adsorption capacity after recycling utilization 5 times is more than the 75% of first time adsorption capacity, it can be extensive Applied to Dye Adsorption separation and waste water from dyestuff pollution control etc..
Description
One, technical field
The present invention relates to a kind of preparation method of magnetic stalk cellulose dye sorbent, magnetism stalk prepared by the present invention
Cellulose dye adsorbent is suitable for the adsorbing separation of dyestuff, can be widely applied to Dye Adsorption, dye separation purification and dye
Expect environmental pollution improvement etc..
Two, background technique
Waste water from dyestuff is mainly derived from dye and dye intermediate production industry and weaving, leather, papermaking, rubber, plastics,
The different industries such as cosmetics, pharmacy and food, with complicated composition, water and change of water quality are big, coloration is high, COD and BOD concentration
High, the features such as suspended matter is more, recalcitrant substance is more, be one of industrial wastewater difficult to deal with.In addition, waste water from dyestuff is not only
Have apparent coloration, influence sense organ, and containing to water body or the poisonous and hazardous pollutant of human body in waste water, if waste water from dyestuff without
Processing direct emission is crossed, the destruction of water ecological setting can be caused, venomous injurant enters food chain, will affect the strong of human body
Health, therefore environment-friendly high-efficiency handles the problem of waste water from dyestuff has become today's society urgent need to resolve.
The method of processing waste water from dyestuff mainly has chemistry, biology, physical method etc. at present.It is easy to operate to precipitate flocculence, at
This is low, but a large amount of sludge generated increase operation cost.Electricity is consumed when Treatment of Wastewater by Electrolysis and metal electrode amount is big.Photocatalysis
Oxidation is only good to low concentration waste water from dyestuff effect.The more single and microorganism of bioanalysis selectivity is environmentally sensitive.Absorption method operation
Simply, at low cost, effect is good, adsorbent is easily recycled.The active charcoal of common adsorbent, mineral, resinae adsorbent
Deng.Activated carbon adsorption power is strong, and removal rate is high, but at high cost, is normally only used for the lower treatment of dyeing wastewater of concentration or depth
Reason.Mineral include natural zeolite, bentonite etc., and ion-exchange capacity and absorption property are preferable, but activity is low, and regeneration is difficult.
And resinae adsorbent treatment effeciency is high, can regenerate under certain condition, can still keep efficiently, being suitable for waste water from dyestuff after regeneration
Processing.
Traditional adsorbent such as ion exchange resin, absorption resin, carbonaceous class adsorbent and natural mesoporous mineral material
Deng can only be separated by conventional methods such as centrifugation, filtering, precipitatings after, these adsorbent materials absorption dyestuff, it is not only time-consuming and laborious and
And not energy-efficient and environmental protection, the structure of destructible adsorbent material affect the regeneration of adsorbent material.In recent years, nanometer
The appearance of material and nanotechnology has been greatly facilitated the progress and development of dyestuff processing technique, and magnetic Nano material is because of its own spy
The advantages that some bigger serfaces, active site abundant and high magnetism, shows huge application in Dye Adsorption and removal field
Potentiality.Magnetic nanometer adsorbent can lead under the action of external magnetic field with the dyestuff contaminant in adsorbed water body, after the completion of absorption
Magnetic Isolation is crossed, realizes the fast and effective separation of adsorbent and mother liquor, and at low cost, it is easy to operate, it preferably solves often
It advises adsorbent and is separated by solid-liquid separation problem difficult and that recycling separation is difficult.
Li et al. utilizes poly- (acrylic acid-acrylamide-butyl methacrylate) hydrogel of Co deposited synthesis magnetism in situ,
There is preferable Adsorption performance to Degradation of Cationic Dye Crystal Violet and basic fuchsin.Xu etc. is changed using solvent structure amino
Property magnetic nano-particle, polyacrylic acid and amino modified magnetic nano-particle be then added carry out chemical graft and prepare magnetic polymeric
Object adsorbent, adsorption capacity 55.8mg/g fast to the rate of adsorption of rhodamine R6G.The synthesis of super branched polyglycereol packet first such as He
Magnetic Fe_3O_4 nanoparticle is covered, butanedioic anhydride is then added and obtains carboxylated modified ultra-branching coated magnetic Fe3O4 nanoparticle
Son is high to dye of positive ion adsorption efficiency, the rate of adsorption is fast, favorable repeatability.Zhou etc. is prepared first with core-shell structure
Then Fe3O4/SiO2 nanoparticle is added dissaving polymer progress surface and is modified, is eventually adding butanedioic anhydride and obtains carboxyl
Change modified ultra-branching coated magnetic Fe3O4/SiO2 nanoparticle, rhodamine R6G and crystal violet adsorption capacity respectively reach
0.37mmol/g and 0.60mmol/g.Chen etc. uses the amino modified Fe3O4 nanoparticle of solvent structure, is then added and hands over
Join agent glutaraldehyde and polyethyleneimine, generates the magnetic polyethylene imines adsorbent with three-dimensional net structure, acid matchmaker's alizarin
Red, methyl orange, methylene blue, sunset yellow, core fast red and Alizarin Green adsorption capacity be respectively 145.7mg/g, 127.5mg/g,
137.0mg/g, 118.3mg/g and 126.8mg/g.
Wen etc. uses 1,2- Bromofume crosslinked polyethylenimine synthesizing polyethylene imine nanometer gel, then using original
The position precipitation method prepare magnetic polyethylene imine nanometer composite hydrogel, and the removal rate of anionic dye CR is more than 99%.Cheng etc.
Using one-step synthesis synthesizing magnetic polyvinyl alcohol/graphene oxide hydrogel, methylene blue and crystal violet adsorption capacity difference
For 231.12mg/g and 204.74mg/g.Shanehsaz etc. prepares magnetic polypyrrole adsorbent, reactive blue using oxidative polymerization method
RB19 adsorption capacity reaches 112.36mg/g.
Hosseinadeh etc. uses one-pot synthesis method to prepare carboxymethyl cellulose and polyacrylic acid as the magnetic fibre of matrix
Element/polyacrylic acid hydrogel, Crystal Violet adsorption capacity reach 189mg/g.Beyki etc. is with the magnetism with core shell structure
Fe3O4- cellulose is added epoxychloropropane and 1- methylimidazole prepares magnetic cellulose ionic liquid adsorbent as matrix,
Congo red adsorption capacity reaches 131mg/g.γ-Fe2O3, cellulose and active carbon are crosslinked by Luo etc. with epoxychloropropane
To magnetic cellulose/acticarbon, to the removal rate of methyl orange and methylene blue more than 99%.Chang etc. is by starch
Then covalence graft multilayer carbon nanotube keeps magnetic nanoparticle raw in starch-grafted carbon nano tube surface by template of starch
It is long, obtain magnetic starch/carbon nanotube adsorption material, methyl orange and methylene blue adsorption number capacity reach respectively 135.8mg/g and
94.1mg/g.Then starch and acrylic monomers is added in the synthesizing magnetic Fe3O4@SiO2 nanoparticle first such as Pourjavadi
It carries out graft copolymerization and prepares magnetic starch graft polyacrylate hydrogel, Crystal Violet Dye removal rate is close to 90%.Baldikova
Deng using sodium citrate-sodium hydroxide modified wheat stalk, magnetic wheat stalk adsorbent is then prepared using microwave process for synthesizing,
Acridine orange and methyl green adsorption capacity are respectively 208.3mg/g and 384.6mg/g.
Although magnetic polymer dye sorbent gets more and more extensive concerning of people and is increasingly becoming both domestic and external grind
Study carefully hot spot, but have not been reported both at home and abroad at present related magnetism stalk cellulose/polyethyleneimine dye sorbent preparation and
Its Dye Adsorption performance study.
Three, summary of the invention
In view of this, the object of the invention is to provide a kind of preparation side of magnetic stalk cellulose dye sorbent
Method.Magnetic nano-particle is prepared using improvement chemical coprecipitation first, table is then carried out to it using Silane coupling agent KH550
Face is modified, obtains KH550 modified magnetic nanoparticle.Stalk is subjected to pretreatment and chemical oxidation prepares aldehyde radical stalk fibre
Then KH550 modified magnetic nanoparticle, aldehyde radical stalk cellulose, polyethyleneimine and glutaraldehyde are chemically crosslinked by element,
Prepare the magnetic stalk cellulose/polyethyleneimine Dye Adsorption with schiff bases cross-linked structure and a variety of Dye Adsorption groups
Agent improves the compatibility of magnetic nano-particle and polymeric matrix by silane coupler modified magnetic nano-particle, inhibits magnetic
Property nanoparticle and polymeric matrix macroface separation, realize the high magnetic of magnetic stalk cellulose adsorbent Dye Adsorption
Intelligence separation preferably solves the disadvantage that common dye adsorbent is separated by solid-liquid separation hardly possible, is also easy to produce secondary pollution.
Purpose according to the present invention proposes a kind of preparation method of magnetic stalk cellulose dye sorbent, feature
There is following processing step:
A) stalk is cut into fragment, be washed with deionized 3~5 times, be put into 60~80 DEG C of baking oven drying, crushed, sieve takes
The stalk powder of 100~200 mesh buffers the Acetic acid-sodium acetate that stalk powder and sodium chlorite are added to pH=3.5~5.5
Solution is warming up to 50~90 DEG C, is cooled to room temperature after reacting 2~6h, filters, and deionized water is washed 3~5 times, centrifuge separation, and 60
~80 DEG C of oven dryings crush, obtain pretreated straw；Stalk powder, sodium chlorite and acetic acid-acetic acid of pH=3.5~5.5
The mass ratio of sodium buffer solution is 10~30:3~10:100~200；
B) pretreated straw is added to the NaOH solution that mass concentration is 5~10%, is warming up to 60~90 DEG C, reaction 2
~6h, filtering, deionized water are washed 3~5 times, and centrifuge separation obtains pretreated straw cellulose；Pretreated straw and quality are dense
Degree is 10~30:100~200 for the mass ratio of 5~10% NaOH solution；
C) pretreated straw cellulose, sodium metaperiodate and deionized water are added in three-necked flask, are warming up to 40~60
DEG C, 1.5~3h is reacted, the mass ratio of pretreated straw cellulose, sodium metaperiodate and deionized water is 10~30:5~10:100
~200；Product is washed with deionized 3~5 times, is centrifugated, obtains aldehyde radical stalk cellulose；
D) FeCl36H2O, FeCl24H2O and deionized water are added in three-necked flask, are stirred evenly, nitrogen is protected
50~80 DEG C are warming up to after shield 30min, the ammonia spirit that mass concentration is 25~30% is then added dropwise, ammonia spirit is added dropwise
3~6h of nitrogen protection isothermal reaction afterwards, FeCl36H2O, FeCl24H2O, the ammonia spirit that mass concentration is 25~30%
Mass ratio with deionized water is 10~30:5~10:25~60:100~200；It is cooled to room temperature, deionized water washing 3~5
Secondary, magnet separation obtains magnetic nano-particle；
E) magnetic nano-particle, Silane coupling agent KH550 and deionized water are added in three-necked flask and are stirred evenly, nitrogen
It is warming up to 50~80 DEG C after gas shielded 30min, the ammonia spirit that mass concentration is 25~30%, nitrogen protection constant temperature is then added dropwise
React 3~6h, magnetic nano-particle, Silane coupling agent KH550, the ammonia spirit that mass concentration is 25~30% and deionized water
Mass ratio be 1~5:2~15:2~15:100~200；It is cooled to room temperature, deionized water is washed 3~5 times, and magnet separation obtains
To KH550 modified Nano magnetic particle；
F) deionized water, KH550 modified magnetic nanoparticle and polyethyleneimine are added in three-necked flask, are passed through nitrogen
Gas agitating is uniform, is warming up to 40~70 DEG C, then addition aldehyde radical stalk cellulose and glutaraldehyde, and nitrogen protection isothermal reaction 1~
3h, aldehyde radical stalk cellulose, KH550 modified magnetic nanoparticle, polyethyleneimine, glutaraldehyde and deionized water mass ratio be
1~6:0.5~5:0.5~5:0.2~2:100~200；Product is washed with deionized 3~5 times, Magnetic Isolation, 60~80
DEG C oven drying crushes, obtains magnetic stalk cellulose dye sorbent；
G) magnetic stalk cellulose dye sorbent saturation magnetization is 10~30emu/g, and remanent magnetism and coercivity become
In zero, there is paramagnetism and magnetic responsiveness, be 100~1000mg/L aqueous dye solutions, Dye Adsorption capacity for initial concentration
Reach 50~300mg/g, 60~150min reaches adsorption equilibrium, and the Dye Adsorption capacity after recycling utilization 5 times is more than the
The 75% of adsorption capacity.
Stalk used in the present invention be selected from corn stover, wheat stalk, soybean stalk, rice straw, broomcorn straw and
Cotton stalk.
Dyestuff used in the present invention is selected from methylene blue, cationic blue FGL, cationic orange R, Cationic Bright Yellow 7GL, sun
The pink FG of ion, methyl green, crystal violet, methyl orange, active black RB5, Congo red, alizarin red, sunset yellow, Alizarin Green, acidic chromium
Blue K and eosin Y.
Advantages of the present invention and effect are:
1) by silane coupler modified magnetic nano-particle, improve the compatible of magnetic nano-particle and polymeric matrix
Property, inhibit the separation of the macroface of magnetic nano-particle and polymeric matrix, realizes magnetic stalk cellulose/polyethyleneimine dyestuff
The high magnetic of absorption intelligently separates, and preferably solves the disadvantage that common adsorbents are separated by solid-liquid separation hardly possible, are also easy to produce secondary pollution.
2) KH550 modified magnetic nanoparticle, aldehyde radical stalk cellulose, polyethyleneimine and glutaraldehyde are subjected to chemical friendship
Connection prepares the magnetic stalk cellulose dye sorbent with schiff bases cross-linked structure and a variety of Dye Adsorption groups, by more
The synergistic effect of kind adsorption group, further increases the absorption property of magnetic stalk cellulose adsorbent dyestuff；
3) magnetic stalk cellulose dye sorbent is prepared with this natural macromolecular material of agricultural crop straw, there is life
Periodic chain is short, it is discarded after can the environmentally protective advantage such as natural degradation, that is, take full advantage of inexhaustible regenerated resources, and solve
The environomental pollution source of crop straw burning realizes farming to current China's crop straw burning and dyestuff bring environmental pollution is administered
The comprehensive utilization of object stalk and agricultural sustainable development have important, have huge social benefit, environmental benefit and economic effect
Benefit.
The hysteresis property of magnetism stalk cellulose dye sorbent of the present invention, Dye Adsorption rate, adsorption capacity,
Recycling utilization performance measurement method is as follows.
The hysteresis property of magnetic stalk cellulose dye sorbent is measured using LDJ-9600 type vibration magnetometer (VSM).
Dry, the finely ground magnetic stalk cellulose dyestuff of dye solution and 0.2g that concentration is 100~1000mg/L is inhaled
Attached dose is put into 250mL conical flask, be subsequently placed in oscillator vibrate absorption, oscillation sample after a certain period of time, using it is ultraviolet/can
Spectrophotometer is seen in the absorbance of dyestuff maximum absorption wave strong point measurement sample, and each sample is measured 3 times and is averaged, dyestuff
Adsorbance qt, adsorption capacity qeIt is calculated as follows respectively:
qt(mg/g)={ (C0-Ct)V}/m (1)
qe(mg/g)={ (C0-Ce)V}/m (2)
Wherein C0、CtAnd CeRespectively dyestuff initial concentration, oscillation absorption certain time dye strength, Dye Adsorption balance
Concentration (mg.L-1), V are liquor capacity (L), and m is the quality (g) of magnetic stalk cellulose dye sorbent.
The magnetic stalk cellulose adsorbent hydrochloric acid solution of 50mL 0.5mol/L of saturation absorption dyestuff is shaken into solution
It inhales, desorption is flat until reaching desorption after a certain period of time using dye strength in ultraviolet/visible spectrophotometer measurement solution
Weighing apparatus.Magnetic stalk cellulose adsorbent after desorption is dried and is crushed, then dyestuff is adsorbed again under the same conditions,
Measure the Dye Adsorption capacity of magnetic stalk cellulose adsorbent using ultraviolet/visible spectrophotometer, and with first time dyestuff
Adsorption capacity compare, characterize the recycling utilization performance of magnetic stalk cellulose dye sorbent, repeated regeneration circulation
The absorption 5 times recycling utilization performances with the magnetic stalk cellulose dye sorbent of assessment.
Four, specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is further explained, but it is of the invention
Content be not limited solely to the following examples.
Embodiment 1:
Corn stover is cut into fragment, is washed with deionized 5 times, 60 DEG C of baking oven drying are put into, is crushed, sieve takes 200 mesh
Maize straw powder, the Acetic acid-sodium acetate that 16g maize straw powder and 6g sodium chlorite are added to 150mL pH=4 is delayed
Solution is rushed, is warming up to 70 DEG C, is cooled to room temperature after reacting 4h, is filtered, deionized water is washed 5 times, centrifuge separation, and 80 DEG C of baking ovens are dry
It is dry, it crushes, obtains pretreatment corn stover；15g pretreatment corn stover is added to the NaOH that 150mL mass concentration is 5%
Solution is warming up to 70 DEG C, reacts 4.5h, filtering, and deionized water is washed 5 times, centrifuge separation, obtains pretreatment corn stalk fiber
Element；25g pretreatment corn stalk fiber element, 10g sodium metaperiodate and 200mL deionized water are added in three-necked flask, heated up
To 50 DEG C, 2.5h is reacted, product is washed with deionized 5 times, be centrifugated, obtains aldehyde radical corn stalk fiber element.
20gFeCl36H2O and 8gFeCl24H2O and 200mL deionized water are added in three-necked flask, stirring is equal
It is even, it is warming up to 70 DEG C after nitrogen protection 30min, the ammonia spirit that 50g mass concentration is 25~30%, ammonia spirit is then added dropwise
Rear nitrogen protection isothermal reaction 4h is added dropwise, is cooled to room temperature, deionized water is washed 4 times, and magnet separation obtains magnetic Nano
Particle；4g magnetic nano-particle, 12g Silane coupling agent KH550 and 200mL deionized water are added in three-necked flask and stirred
It is even, it is warming up to 80 DEG C after nitrogen protection 30min, the ammonia spirit that 12g mass concentration is 25~30%, nitrogen protection is then added dropwise
Room temperature is cooled to after isothermal reaction 3h, deionized water is washed 3 times, and magnet separation obtains KH550 modified Nano magnetic particle.
200mL deionized water, 4g KH550 modified magnetic nanoparticle and 4g polyethyleneimine are added to three-necked flask
In, it is uniform to be passed through nitrogen gas stirring, is warming up to 60 DEG C, and 4g aldehyde radical corn stalk fiber element and 1.8g glutaraldehyde, nitrogen is then added
Isothermal reaction 1.5h is protected, product is washed with deionized 5 times, Magnetic Isolation, 80 DEG C of oven dryings, crushes, obtains magnetism
Corn stalk fiber element dye sorbent, saturation magnetization are 10~30emu/g, and remanent magnetism and coercivity go to zero, have
Paramagnetism and magnetic responsiveness；Crystal violet, Cationic Bright Yellow 7GL, active black RB5 and the methyl for being 1000mg/L for initial concentration
Orange aqueous solution, magnetic corn stalk fiber element dye sorbent crystal violet, Cationic Bright Yellow 7GL, active black RB5 and methyl orange are inhaled
Attached capacity respectively reaches 300mg/g, 228mg/g, 150mg/g and 125mg/g, and 60min reaches adsorption equilibrium, recycling utilization
Crystal violet, Cationic Bright Yellow 7GL, active black RB5 and Adsorption of Methyl Orange capacity after 5 times are more than first time adsorption capacity
75%.
Embodiment 2:
Wheat stalk is cut into fragment, is washed with deionized 3 times, 80 DEG C of baking oven drying are put into, is crushed, sieve takes 150 mesh
Wheat stalk powder, 12g wheat stalk powder and 3.5g sodium chlorite are added to acetic acid-acetic acid of 100mL pH=5.5
Sodium buffer solution is warming up to 70 DEG C, is cooled to room temperature after reacting 4h, filters, and deionized water is washed 5 times, centrifuge separation, 80 DEG C of bakings
Case dry, pulverize, and obtain pretreatment wheat stalk；It is 10% that 12g pretreatment wheat stalk, which is added to 100mL mass concentration,
NaOH solution is warming up to 80 DEG C, reacts 3h, filtering, and deionized water is washed 5 times, centrifuge separation, and it is fine to obtain pretreatment wheat stalk
Dimension element；12g pretreatment wheat straw fiber element, 6g sodium metaperiodate and 100mL deionized water are added in three-necked flask, heated up
To 50 DEG C, 2.5h is reacted, product is washed with deionized 5 times, be centrifugated, obtains aldehyde radical wheat straw fiber element.
15gFeCl36H2O and 6gFeCl24H2O and 150mL deionized water are added in three-necked flask, stirring is equal
It is even, it is warming up to 50 DEG C after nitrogen protection 30min, the ammonia spirit that 35g mass concentration is 25~30%, ammonia spirit is then added dropwise
Rear nitrogen protection isothermal reaction 6h is added dropwise, is cooled to room temperature, deionized water is washed 5 times, and magnet separation obtains magnetic Nano
Particle；2.5g magnetic nano-particle, 5g Silane coupling agent KH550 and 100mL deionized water are added in three-necked flask and are stirred
Uniformly, 50 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that 6g mass concentration is 25~30% is then added dropwise, nitrogen is protected
Room temperature is cooled to after shield isothermal reaction 6h, deionized water is washed 5 times, and magnet separation obtains KH550 modified Nano magnetic particle.
100mL deionized water, 1.5g KH550 modified magnetic nanoparticle and 3g polyethyleneimine are added to three mouthfuls of burnings
In bottle, it is uniform to be passed through nitrogen gas stirring, is warming up to 60 DEG C, and 4g aldehyde radical wheat straw fiber element and 1g glutaraldehyde, nitrogen is then added
Isothermal reaction 1.5h is protected, product is washed with deionized 3 times, Magnetic Isolation, 60 DEG C of oven dryings, crushes, obtains magnetism
Wheat straw fiber element dye sorbent, saturation magnetization 10emu/g, remanent magnetism and coercivity go to zero, and have paramagnetic
Property and magnetic responsiveness；Cationic Bright Yellow 7GL, active black RB5, alizarin red and the sunset yellow water for being 800mg/L for initial concentration
Solution, magnetic wheat straw fiber element dye sorbent Cationic Bright Yellow 7GL, active black RB5, alizarin red and sunset yellow absorption are held
Amount respectively reaches 193mg/g, 120mg/g, 98mg/g and 86mg/g, and 80min reaches adsorption equilibrium, after recycling utilization 5 times
Cationic Bright Yellow 7GL, active black RB5, alizarin red and sunset yellow adsorption capacity be more than the 75% of first time adsorption capacity.
Embodiment 3:
Broomcorn straw is cut into fragment, is washed with deionized 3 times, 60 DEG C of baking oven drying are put into, is crushed, sieve takes 150 mesh
Broomcorn straw powder, 30g broomcorn straw powder and 10g sodium chlorite are added to the Acetic acid-sodium acetate of 200mL pH=3.5
Buffer solution is warming up to 90 DEG C, is cooled to room temperature after reacting 2h, filters, and deionized water is washed 5 times, centrifuge separation, 80 DEG C of baking ovens
It dry, pulverize, obtain pretreatment broomcorn straw；It is 5% that 15g pretreatment broomcorn straw, which is added to 150mL mass concentration,
NaOH solution is warming up to 60 DEG C, reacts 6h, filtering, and deionized water is washed 5 times, centrifuge separation, and it is fine to obtain pretreatment broomcorn straw
Dimension element；20g is pre-processed broomcorn straw cellulose, 8g sodium metaperiodate and 150mL deionized water to be added in three-necked flask, is heated up
To 40 DEG C, 3h is reacted, product is washed with deionized 5 times, is centrifugated, obtain aldehyde radical broomcorn straw cellulose.
10gFeCl36H2O and 5gFeCl24H2O and 100mL deionized water are added in three-necked flask, stirring is equal
It is even, it is warming up to 80 DEG C after nitrogen protection 30min, the ammonia spirit that 25g mass concentration is 25~30%, ammonia spirit is then added dropwise
Rear nitrogen protection isothermal reaction 3h is added dropwise, is cooled to room temperature, deionized water is washed 4 times, and magnet separation obtains magnetic Nano
Particle；3g magnetic nano-particle, 8g Silane coupling agent KH550 and 150mL deionized water are added in three-necked flask and stirred
It is even, it is warming up to 80 DEG C after nitrogen protection 30min, the ammonia spirit that 10g mass concentration is 25~30%, nitrogen protection is then added dropwise
Room temperature is cooled to after isothermal reaction 3h, deionized water is washed 3 times, and magnet separation obtains KH550 modified Nano magnetic particle.
150mL deionized water, 5g KH550 modified magnetic nanoparticle and 2g polyethyleneimine are added to three-necked flask
In, it is uniform to be passed through nitrogen gas stirring, is warming up to 40 DEG C, and 3g aldehyde radical broomcorn straw cellulose and 1g glutaraldehyde is then added, and nitrogen is protected
Isothermal reaction 3h is protected, product is washed with deionized 5 times, Magnetic Isolation, 80 DEG C of oven dryings, crushes, obtains magnetic sorghum
Stalk cellulose dye sorbent, saturation magnetization 30emu/g, remanent magnetism and coercivity go to zero, have paramagnetism and
Magnetic responsiveness；Crystal violet, methylene blue, sunset yellow and the Alizarin Green aqueous solution for being 600mg/L for initial concentration, magnetic sorghum
Stalk cellulose dye sorbent crystal violet, methylene blue, sunset yellow and Alizarin Green adsorption capacity respectively reach 150mg/g,
100mg/g, 85mg/g and 72mg/g, 100min reach adsorption equilibrium, crystal violet, methylene blue after recycling utilization 5 times,
Sunset yellow and Alizarin Green adsorption capacity are more than the 75% of first time adsorption capacity.
Embodiment 4:
Soybean stalk is cut into fragment, is washed with deionized 5 times, 80 DEG C of baking oven drying are put into, is crushed, sieve takes 200 mesh
Soybean stalk powder, 15g soybean stalk powder and 4g sodium chlorite are added to the Acetic acid-sodium acetate of 150mL pH=4.8
Buffer solution is warming up to 50 DEG C, is cooled to room temperature after reacting 6h, filters, and deionized water is washed 5 times, centrifuge separation, 60 DEG C of baking ovens
It dry, pulverize, obtain pretreated soybean stalk；It is 10% that 30g pretreated soybean stalk, which is added to 200mL mass concentration,
NaOH solution is warming up to 90 DEG C, reacts 2h, filtering, and deionized water is washed 5 times, and it is fine to obtain pretreated soybean stalk for centrifuge separation
Dimension element；30g pretreated soybean stalk cellulose, 10g sodium metaperiodate and 200mL deionized water are added in three-necked flask, risen
Temperature reacts 1.5h, product is washed with deionized 5 times to 60 DEG C, is centrifugated, obtains aldehyde radical soybean stalk cellulose.
30gFeCl36H2O and 10gFeCl24H2O and 200mL deionized water are added in three-necked flask, stirred
Uniformly, 70 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that 60g mass concentration is 25~30% is then added dropwise, ammonium hydroxide is molten
Rear nitrogen protection isothermal reaction 4h is added dropwise in liquid, is cooled to room temperature, and deionized water is washed 5 times, and magnet separation obtains magnetism and receives
Rice corpuscles；5g magnetic nano-particle, 15g Silane coupling agent KH550 and 200mL deionized water are added in three-necked flask and are stirred
Uniformly, 70 DEG C are warming up to after nitrogen protection 30min, the ammonia spirit that 15g mass concentration is 25~30% is then added dropwise, nitrogen is protected
Room temperature is cooled to after shield isothermal reaction 4h, deionization is washed 5 times or so, and magnet separation obtains KH550 modified Nano magnetic particles
Son.
200mL deionized water, 5g KH550 modified magnetic nanoparticle and 5g polyethyleneimine are added to three-necked flask
In, it is uniform to be passed through nitrogen gas stirring, is warming up to 70 DEG C, and 6g aldehyde radical soybean stalk cellulose and 2g glutaraldehyde is then added, and nitrogen is protected
Isothermal reaction 1h is protected, product is washed with deionized 5 times, Magnetic Isolation, 60 DEG C of oven dryings, crushes, obtains magnetic soybean
Stalk cellulose dye sorbent, saturation magnetization 18.6emu/g, remanent magnetism and coercivity go to zero, and have paramagnetism
And magnetic responsiveness；Methylene blue, methyl green, active black RB5 and the Alizarin Red Aqueous Solution for being 300mg/L for initial concentration, magnetic
Property soybean stalk cellulose dye adsorbent methylene blue, methyl green, active black RB5 and alizarin red adsorption capacity respectively reach
82mg/g, 77mg/g, 72mg/g and 60mg/g, 120min reach adsorption equilibrium, methylene blue after recycling utilization 5 times,
Methyl green, active black RB5 and alizarin red adsorption capacity are more than the 75% of first time adsorption capacity.
Embodiment 5:
Cotton stalk is cut into fragment, is washed with deionized 3 times, 60 DEG C of baking oven drying are put into, is crushed, sieve takes 100 mesh
Cotton stalk powder, 10g cotton stalk powder and 3g sodium chlorite are added to the Acetic acid-sodium acetate of 100mL pH=4.5
Buffer solution is warming up to 80 DEG C, is cooled to room temperature after reacting 3h, filters, and deionized water is washed 3 times, centrifuge separation, 80 DEG C of baking ovens
It dry, pulverize, obtain pretreatment cotton stalk；It is 10% that 10g pretreatment cotton stalk, which is added to 100mL mass concentration,
NaOH solution is warming up to 80 DEG C, reacts 3h, filtering, and deionized water is washed 3 times, centrifuge separation, and it is fine to obtain pretreatment cotton stalk
Dimension element；10g pretreatment producing fibre from cotton stalk element, 5g sodium metaperiodate and 100mL deionized water are added in three-necked flask, heated up
To 55 DEG C, 2h is reacted, product is washed with deionized 3 times, be centrifugated, obtains aldehyde radical producing fibre from cotton stalk element.
19.6g FeCl36H2O and 7.2g FeCl24H2O and 150mL deionized water is added in three-necked flask,
It stirs evenly, 60 DEG C is warming up to after nitrogen protection 30min, the ammonia spirit that 50g mass concentration is 25~30%, ammonia is then added dropwise
Rear nitrogen protection isothermal reaction 5h is added dropwise in aqueous solution, is cooled to room temperature, and deionized water is washed 3 times, and magnet separation obtains magnetic
Property nanoparticle；1g magnetic nano-particle, 2g Silane coupling agent KH550 and 100mL deionized water are added in three-necked flask
It stirs evenly, 60 DEG C is warming up to after nitrogen protection 30min, the ammonia spirit that 2g mass concentration is 25~30%, nitrogen is then added dropwise
Room temperature is cooled to after gas shielded isothermal reaction 5h, deionized water is washed 5 times, and magnet separation obtains KH550 modified Nano magnetic particles
Son.
100mL deionized water, 0.5g KH550 modified magnetic nanoparticle and 0.5g polyethyleneimine are added to three mouthfuls
In flask, it is uniform to be passed through nitrogen gas stirring, is warming up to 50 DEG C, and 1g aldehyde radical producing fibre from cotton stalk element and 0.2g glutaraldehyde is then added,
Nitrogen protection isothermal reaction 2h product is washed with deionized 3 times, Magnetic Isolation, 80 DEG C of oven dryings, crushes, obtains magnetic
Property producing fibre from cotton stalk element dye sorbent, saturation magnetization 15.2emu/g, remanent magnetism and coercivity go to zero, have
Paramagnetism and magnetic responsiveness；Crystal violet, Cationic Bright Yellow 7GL, sunset yellow and the alizarin clear water for being 100mg/L for initial concentration
Solution, magnetic producing fibre from cotton stalk element dye sorbent crystal violet, Cationic Bright Yellow 7GL, methyl orange and Congo red adsorption capacity
73mg/g, 68mg/g, 54mg/g and 50mg/g are respectively reached, 150min reaches adsorption equilibrium, the knot after recycling utilization 5 times
Crystalviolet, Cationic Bright Yellow 7GL, methyl orange and Congo red adsorption capacity are more than the 75% of first time adsorption capacity.
Claims (3)
1. a kind of preparation method of magnetism stalk cellulose dye sorbent, it is characterised in that there is following processing step:
A) stalk being cut into fragment, be washed with deionized 3~5 times, be put into 60~80 DEG C of baking oven drying, crushed, sieve takes 100~
Stalk powder and sodium chlorite are added to the NaAc_HAc buffer solution of pH=3.5~5.5 by the stalk powder of 200 mesh,
50~90 DEG C are warming up to, is cooled to room temperature after reacting 2~6h, is filtered, deionized water is washed 3~5 times, centrifuge separation, and 60~80
DEG C oven drying crushes, obtains pretreated straw；Stalk powder, sodium chlorite and the Acetic acid-sodium acetate of pH=3.5~5.5 are slow
The mass ratio for rushing solution is 10~30:3~10:100~200；
B) pretreated straw is added to the NaOH solution that mass concentration is 5~10%, is warming up to 60~90 DEG C, react 2~6h,
Filtering, deionized water are washed 3~5 times, and centrifuge separation obtains pretreated straw cellulose；Pretreated straw and mass concentration are 5
The mass ratio of~10% NaOH solution is 10~30:100~200；
C) pretreated straw cellulose, sodium metaperiodate and deionized water are added in three-necked flask, are warming up to 40~60 DEG C, instead
1.5~3h is answered, the mass ratio of pretreated straw cellulose, sodium metaperiodate and deionized water is 10~30:5~10:100~200；
Product is washed with deionized 3~5 times, is centrifugated, obtains aldehyde radical stalk cellulose；
D) FeCl36H2O, FeCl24H2O and deionized water are added in three-necked flask, are stirred evenly, nitrogen protection
It is warming up to 50~80 DEG C after 30min, the ammonia spirit that mass concentration is 25~30% is then added dropwise, after ammonia spirit is added dropwise
Nitrogen protection isothermal reaction 3~6h, FeCl36H2O, FeCl24H2O, mass concentration be 25~30% ammonia spirit and
The mass ratio of deionized water is 10~30:5~10:25~60:100~200；It is cooled to room temperature, deionized water is washed 3~5 times,
Magnet separation, obtains magnetic nano-particle；
E) magnetic nano-particle, Silane coupling agent KH550 and deionized water are added in three-necked flask and are stirred evenly, nitrogen is protected
50~80 DEG C are warming up to after shield 30min, the ammonia spirit that mass concentration is 25~30%, nitrogen protection isothermal reaction is then added dropwise
3~6h, the matter of magnetic nano-particle, Silane coupling agent KH550, the ammonia spirit that mass concentration is 25~30% and deionized water
Amount is than being 1~5:2~15:2~15:100~200；It is cooled to room temperature, deionized water is washed 3~5 times, and magnet separation obtains
KH550 modified Nano magnetic particle；
F) deionized water, KH550 modified magnetic nanoparticle and polyethyleneimine are added in three-necked flask, are passed through nitrogen and stir
It mixes uniformly, is warming up to 40~70 DEG C, aldehyde radical stalk cellulose and glutaraldehyde, nitrogen protection 1~3h of isothermal reaction, aldehyde is then added
Base stalk cellulose, KH550 modified magnetic nanoparticle, polyethyleneimine, glutaraldehyde and deionized water mass ratio be 1~6:
0.5~5:0.5~5:0.2~2:100~200；Product is washed with deionized 3~5 times, Magnetic Isolation, 60~80 DEG C of bakings
Case dry, pulverize, and obtain magnetic stalk cellulose dye sorbent；
G) magnetic stalk cellulose dye sorbent saturation magnetization is 10~30emu/g, and remanent magnetism and coercivity go to zero,
It is 100~1000mg/L aqueous dye solutions for initial concentration with paramagnetism and magnetic responsiveness, Dye Adsorption capacity reaches 50
~300mg/g, 60~150min reach adsorption equilibrium, and the Dye Adsorption capacity after recycling utilization 5 times is more than to inhale for the first time
The 75% of attached capacity.
2. a kind of preparation method of magnetic stalk cellulose dye sorbent according to claim 1, it is characterised in that: institute
The stalk stated is selected from corn stover, wheat stalk, soybean stalk, rice straw, jowar stalk and cotton stalk.
3. a kind of preparation method of magnetic stalk cellulose dye sorbent according to claim 1, it is characterised in that: institute
The dyestuff stated be selected from methylene blue, cationic blue FGL, cationic orange R, Cationic Bright Yellow 7GL, cationic pink fg, methyl green,
Crystal violet, methyl orange, active black RB5, Congo red, alizarin red, sunset yellow, Alizarin Green, acid chromium blue k and eosin Y.
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| CN110833820B (en) * | 2019-10-23 | 2023-06-09 | 浙江理工大学 | Preparation method of cellulose nanofiber-based reusable environment restoration material capable of adsorbing heavy metal ions and dyes |
| CN110898817A (en) * | 2019-11-29 | 2020-03-24 | 南昌大学 | Preparation method and application of polyethyleneimine modified magnetic bamboo powder material |
| CN111468071B (en) * | 2020-04-09 | 2022-09-20 | 中冶华天工程技术有限公司 | Rapid preparation method of magnetically separable composite adsorption material |
| CN111482161B (en) * | 2020-04-17 | 2021-04-16 | 青岛理工大学 | Magnetic biological manganese oxide adsorption material and preparation and application thereof |
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| CN113318784B (en) * | 2021-05-27 | 2022-07-05 | 昆明理工大学 | Preparation method and application of corn straw loaded nano osmium composite filter column |
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| CN114934386B (en) * | 2022-02-25 | 2024-08-23 | 浙江理工大学 | P-N-Si organic-inorganic hybrid flame-retardant cotton fabric and preparation method thereof |
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| CN103881033A (en) * | 2014-02-26 | 2014-06-25 | 成都理工大学 | Preparation method of crop straw dye adsorption material |
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