CN114870905A - Method for in-situ preparation of titanium dioxide/cellulose nano composite microspheres - Google Patents
Method for in-situ preparation of titanium dioxide/cellulose nano composite microspheres Download PDFInfo
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- CN114870905A CN114870905A CN202210640061.9A CN202210640061A CN114870905A CN 114870905 A CN114870905 A CN 114870905A CN 202210640061 A CN202210640061 A CN 202210640061A CN 114870905 A CN114870905 A CN 114870905A
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- cellulose
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229920002678 cellulose Polymers 0.000 title claims abstract description 75
- 239000001913 cellulose Substances 0.000 title claims abstract description 75
- 239000004005 microsphere Substances 0.000 title claims abstract description 60
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 60
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 20
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 27
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 27
- 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 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 235000010980 cellulose Nutrition 0.000 claims description 71
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 14
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 11
- 229940057995 liquid paraffin Drugs 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000007762 w/o emulsion Substances 0.000 claims description 5
- 238000004065 wastewater treatment Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- -1 iron ions Chemical class 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 2
- 229920001046 Nanocellulose Polymers 0.000 claims description 2
- 239000005016 bacterial cellulose Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 238000001879 gelation Methods 0.000 claims description 2
- 239000004021 humic acid Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- 239000002121 nanofiber Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 31
- 230000015556 catabolic process Effects 0.000 abstract description 29
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 5
- 238000004945 emulsification Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000499 gel Substances 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000000017 hydrogel Substances 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 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 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000004098 Tetracycline Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229960002180 tetracycline Drugs 0.000 description 3
- 229930101283 tetracycline Natural products 0.000 description 3
- 235000019364 tetracycline Nutrition 0.000 description 3
- 150000003522 tetracyclines Chemical class 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/28016—Particle form
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/28014—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 form
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- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
A method for preparing titanium dioxide/cellulose nano composite microspheres in situ is characterized in that prehydrolyzed n-butyl titanate solution is added into cellulose solution to obtain prefabricated solution, and the nano composite cellulose microspheres of in-situ mineralized amorphous titanium dioxide are prepared by an inverse emulsion method. The amorphous titanium dioxide prepared by the method can expose more active sites, and the adsorption performance of the amorphous titanium dioxide is far higher than that of microspheres prepared by the traditional blending method. The composite microspheres show the characteristic of accelerated degradation efficiency in the degradation process of rhodamine B. The invention has wide substrate source, environmental protection, nontoxic solvent system, low price, simple material preparation process, easy mastering of process, low production cost and huge potential of large-scale production.
Description
Technical Field
The invention relates to the technical field of preparation of nano composite gel microspheres for water treatment, in particular to a preparation method of a composite catalyst which is prepared in situ, has high adsorption and easy sensitization and can efficiently degrade pollutants in water.
Background
The photocatalysis technology converts light energy into chemical energy through semiconductor nano materials, and the generated free radicals can efficiently degrade and mineralize pollutants in water, so the photocatalysis technology is widely applied to wastewater treatment. Among numerous photocatalysts, titanium dioxide has gained wide attention in both academic research and practical application due to the advantages of abundant reserves, low cost, easy preparation and the like. However, efficient photocatalytic reactions require that carriers generated by the semiconductor material under illumination can reach the catalyst surface efficiently. This requires that the size of the catalyst be small enough to shorten the carrier transport distance and reduce photoinduced carrier recombination. However, in practical application, the problem that the recovery of the nano-sized titanium dioxide is difficult not only leads to the increase of the cost, but also has certain harm to the environment. One of the effective ways to solve the problem of recovering nano titania is to load it on a carrier while maintaining sufficient exposure of the active sites of the catalyst.
Compared with other types of carriers, the hydrogel is considered to be an effective carrier for supporting the titanium dioxide photocatalyst and improving the recovery performance of the titanium dioxide photocatalyst due to the unique three-dimensional network of the hydrogel. Cellulose is a biomass material with the largest reserve and has the advantages of being green and renewable. Meanwhile, a large number of hydrogen bonds in cellulose molecules and among the molecules can construct a hydrophilic three-dimensional network, and the cellulose gel preparation material is potential. The cellulose hydrogel microspheres prepared by the methods of inverse emulsion, precipitation bath and the like can shorten the transmission distance of pollutants in hydrogel due to the micron-sized size, and have wide application prospect in wastewater treatment.
The Chinese patent document discloses a composite nano titanium dioxide and a preparation method thereof (CN 200710307861.4): the nano titanium dioxide and the water solution of water-soluble cellulose are contacted with polymerizable monomers under the condition of an initiator. The cellulose is methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, and hydroxypropyl methylcellulose. The polymerizable monomers are methyl methacrylate, butyl acrylate and methacrylic acid.
The high surface energy of the nanoparticles makes it difficult to obtain highly dispersed titanium dioxide/cellulose composite microspheres by conventional blending methods. The agglomerated nano particles in the hydrogel are more easily embedded into a gel network structure, so that the exposed active sites are greatly reduced, and the photocatalytic activity of the hydrogel is reduced. Therefore, how to balance the structural stability of the catalyst/hydrogel and the photocatalytic performance of the catalyst is of great significance to the practical application of the photocatalyst in wastewater treatment.
Disclosure of Invention
The invention aims to provide a method for preparing titanium dioxide/cellulose nano composite microspheres in situ, aiming at enabling highly dispersed titanium dioxide to have higher specific surface area, expose more active sites and have better photocatalysis.
The purpose of the invention is realized as follows: a method for preparing titanium dioxide/cellulose nano composite microspheres in situ is characterized by comprising the following steps:
(1) preparing prehydrolysis liquid of n-butyl titanate: mixing n-butyl titanate and triethanolamine at room temperature, dropwise adding deionized water into the mixed solution, and reacting to obtain prehydrolysis liquid;
(2) preparing a gel prefabricated liquid: dissolving lithium hydroxide and urea by using deionized water, and freezing; adding the dried cellulose into the frozen mixed solvent, and adding the n-butyl titanate prehydrolysis liquid obtained in the step (1) under the stirring condition to obtain a stable n-butyl titanate prehydrolysis liquid/cellulose mixed solution;
(3) preparing titanium dioxide/cellulose microspheres: adding span 80 serving as a surfactant into liquid paraffin, uniformly stirring, adding the gel prefabricated liquid obtained in the step (2), stirring to obtain a water-in-oil emulsion, and gelatinizing the emulsion at room temperature to obtain the titanium dioxide/cellulose microspheres.
In the step (1), the molar ratio of n-butyl titanate to triethanolamine is 0.01-10.0; the concentration of the n-butyl titanate is 0.1 mol/L-5 mol/L.
In the step (1), the deionized water can be replaced by a metal cation (iron ions, silver ions and the like) solution or a non-metal anion (sodium lignosulfonate, humic acid and the like) solution; in the step (2), the cellulose dissolving system can also be a sodium hydroxide/urea/thiourea system, a sodium hydroxide/lithium chloride/urea system or a sodium hydroxide/urea system;
in the step (2), the cellulose may be native cellulose, bacterial cellulose, microcrystalline cellulose, nanocellulose (cellulose nanocrystal and cellulose nanofiber), and water-soluble diffraction cellulose (carboxymethyl cellulose).
In the step (2), the mass fraction of the cellulose in the solution is 0.01-10 wt%; in the step (2), the mass ratio of the n-butyl titanate prehydrolysis liquid to the cellulose solution is as follows: 0.01 to 0.5; in the step (3), the volume ratio of the liquid paraffin to the gel prefabricated liquid is as follows: 1-100; in the step (3), the mass-to-volume ratio of span 80 to the emulsion is as follows: 0.01 to 0.5.
In the step (3), the stirring mode of the emulsion preparation can be mechanical stirring or stirring by using an emulsion homogenizer, and the rotating speed is 300-30000 rpm.
In the step (3), the gelation temperature of the emulsion is 0-80 ℃.
A modification method of the titanium dioxide/cellulose nano composite microspheres comprises the following steps:
(1) preparing a rhodamine B solution: weighing a certain amount of rhodamine B, dissolving the rhodamine B with deionized water, and fixing the volume for later use;
(2) degrading an intermediate modified microsphere by using rhodamine B: adding the microspheres in the claim 1 into a rhodamine B solution, adding a certain amount of hydrogen peroxide, degrading the rhodamine B under the illumination condition, and obtaining the modified microspheres through settling separation after the solution is colorless and transparent.
A composite microsphere and an application of a modified microsphere in wastewater treatment.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, n-butyl titanate prehydrolysis liquid is added into the cellulose solution, and the obtained homogeneous solution successfully avoids the problem of agglomeration caused by high surface energy of nano particles. Highly dispersed titanium dioxide has a higher specific surface area and exposes more active sites. For methylene blue solution with initial concentration of 10mg/L, the adsorption capacity of the in-situ mineralized titanium dioxide/cellulose microspheres is 20mg/g, which is far higher than that of the commercial titanium dioxide blended microspheres by 3.0 mg/g.
(2) The high-dispersion amorphous titanium dioxide has more exposed active sites and abundant surface hydroxyl groups, and can sensitize titanium dioxide by a degradation intermediate product in the degradation process of rhodamine B to accelerate the catalytic efficiency of the titanium dioxide, wherein the degradation rate is 0.0582min in two-round degradation -1 0.0487min higher than that of commercial titanium dioxide blended microspheres -1 The degradation rate of (a). Meanwhile, sensitization of the rhodamine B degradation intermediate on titanium dioxide can still play a role in improving degradation efficiency in degradation of mixed pollutants.
(3) The titanium dioxide generated in situ can be modified by adding metal cations or non-metal anions into the n-butyl titanate prehydrolysis liquid to prepare the titanium dioxide/cellulose microspheres with visible light response or optimized electron transfer characteristics.
(4) The invention takes cellulose as a matrix, and the cellulose is wide in source and environment-friendly; the nano titanium dioxide is used as a filler, so that the photocatalysis performance is excellent, and the cost is lower; the alkaline urea solvent system is non-toxic, environment-friendly and low in cost; the preparation process of the material is easy to master and has great potential for large-scale production.
The invention takes environment-friendly cellulose with wide sources as a matrix and n-butyl titanate as a titanium source, introduces nano titanium dioxide in situ in a cellulose network, and prepares the titanium dioxide/cellulose nano composite hydrogel microspheres by a reverse emulsion method. The invention overcomes the problem of nanoparticle dispersion existing in the existing blending method by an in-situ mineralization method. The highly dispersed in-situ mineralized titanium dioxide/cellulose microspheres have more active sites, show higher adsorption performance than microspheres prepared by blending commercial titanium dioxide, and can utilize a broader-spectrum light source to obtain higher degradation efficiency by sensitizing rhodamine B degradation intermediates. From the patent of the current application and the published literature of the gel-supported photocatalyst, it is not reported that the nano composite microsphere obtained by introducing titanium dioxide in situ in a homogeneous system is used for efficiently degrading dye pollutants in water.
Drawings
FIG. 1 shows the microstructure of comparative example 1(a), comparative example 2(b) and example 1(c) under an optical microscope.
FIG. 2 is a scanning electron microscope image of the microstructure of comparative example 2(a) and example 1 (b).
FIG. 3 is a comparison of the adsorption performance of comparative example 2 and example 1 for methylene blue.
FIG. 4 is a comparison of the degradation performance of rhodamine B under the ultraviolet light condition of the comparative example 2 and the example 1.
FIG. 5 shows the rhodamine B cyclic degradation test under the ultraviolet light condition in example 1.
FIG. 6 shows the UV-VIS diffuse reflectance spectra of comparative example 2, example 1 and example 2
Fig. 7 is a comparison of the degradation performance of comparative example 2 and example 2 on tetracycline under visible light conditions.
Detailed Description
The following examples are given to illustrate the present invention and it should be noted that the following examples are given only for the purpose of further illustrating the present invention and should not be construed as limiting the scope of the present invention. The preparation process mainly comprises two parts of preparation of n-butyl titanate prehydrolysis liquid and preparation of in-situ titanium dioxide/cellulose microspheres.
Example 1
A method for preparing titanium dioxide/cellulose nano composite microspheres in situ uses the following raw materials and reagents:
raw materials: primary cellulose (cotton linters, degree of polymerization 500), n-butyl titanate reagent: the preparation method of the lithium hydroxide, the urea, the triethanolamine, the span 80, the liquid paraffin and the deionized water comprises the following steps:
(1) preparing prehydrolysis liquid of n-butyl titanate: mixing n-butyl titanate and triethanolamine at room temperature according to a molar ratio of 1:2, dropwise adding deionized water into the mixed solution, and reacting to obtain prehydrolysis solution, wherein the final concentration of the n-butyl titanate is 1.25 mol/L;
(2) preparing a gel prefabricated liquid: dissolving lithium hydroxide and urea with deionized water, and freezing. Adding 2.57g of dried cellulose into 100g of frozen mixed solvent, and adding 5.0mL of n-butyl titanate prehydrolysis liquid obtained in the step (1) under the stirring condition to obtain stable n-butyl titanate prehydrolysis liquid/cellulose mixed solution; (3) preparing titanium dioxide/cellulose microspheres: 4.0g of span 80 as a surfactant is added into 120mL of liquid paraffin, the mixture is stirred uniformly, 40mL of the gel preformance prepared in the step (2) is added, and water-in-oil emulsion is obtained under the stirring condition of 800 rpm. The emulsion is gelatinized for 2 hours at the temperature of 25 ℃ to obtain the titanium dioxide/cellulose microspheres.
Example 2
A modification method of titanium dioxide/cellulose nano composite microspheres prepared in situ comprises the following raw materials and reagents:
raw materials: example 1 microspheres
Reagent: rhodamine B, hydrogen peroxide and deionized water
The preparation method comprises the following steps:
(1) preparing a rhodamine B solution: weighing a certain amount of rhodamine B, dissolving the rhodamine B with deionized water, and fixing the volume for later use;
(2) degrading an intermediate modified microsphere by using rhodamine B: the microspheres in the embodiment 1 are added into a rhodamine B solution, a certain amount of hydrogen peroxide is added, and degradation of rhodamine B is carried out under the illumination condition. And when the solution is colorless and transparent, settling and separating to obtain the modified microspheres.
Examples 3-20 are shown in Table 1:
TABLE 1 preparation conditions of examples 3 to 20
Table 2 comparison table of sizes, titanium dioxide loading amounts, adsorption performances and degradation performances of examples 3-20
Degradation time was 70 minutes.
Comparative example 1
A method for preparing cellulose microspheres uses the following raw materials and reagents:
raw materials: virgin cellulose (Cotton linter, degree of polymerization 500)
Reagent: lithium hydroxide, urea, span 80, liquid paraffin and deionized water
The preparation method comprises the following steps:
(1) preparing a gel prefabricated liquid: dissolving lithium hydroxide and urea with deionized water, and freezing. Adding the dried cellulose into the frozen mixed solvent, and stirring to obtain a cellulose solution;
(2) preparing cellulose microspheres: adding span 80 serving as a surfactant into liquid paraffin, uniformly stirring, adding the gel prefabricated liquid obtained in the step (1), and stirring to obtain a water-in-oil emulsion. The emulsion is gelatinized at room temperature to obtain the cellulose microspheres.
Comparative example 2
A method for preparing titanium dioxide/cellulose nano composite microspheres by blending comprises the following raw materials and reagents:
raw materials: native cellulose (cotton linter, degree of polymerization 500), titanium dioxide nanoparticles (anatase)
Reagent: lithium hydroxide, urea, span 80, liquid paraffin and deionized water
The preparation method comprises the following steps:
(1) preparing a gel prefabricated liquid: after lithium hydroxide and urea were dissolved in deionized water, titanium dioxide nanoparticles having the same mass as in example 1 were added, and the mixture was frozen. Adding the dried cellulose into the frozen mixed solvent, and stirring to obtain a titanium dioxide/cellulose dispersion liquid;
(2) preparing titanium dioxide/cellulose microspheres: adding span 80 serving as a surfactant into liquid paraffin, uniformly stirring, adding the gel prefabricated liquid obtained in the step (1), and stirring to obtain a water-in-oil emulsion. The emulsion is gelatinized at room temperature to obtain the titanium dioxide/cellulose microspheres.
And (3) appearance observation: as shown in FIG. 1, the example and comparative example 1 are semitransparent and comparative example 2 is opaque under an optical microscope, which shows that the titanium dioxide nanoparticles in comparative example 2 are agglomerated and have a size larger than a visible light band, thereby causing black and opaque in a microscope view. In order to examine the dispersion of titanium dioxide in the example and the proportion 2 on a more microscopic level, the freeze-dried samples were respectively characterized by scanning electron microscopy (FIG. 2). In the scanning electron micrograph, the surface of comparative example 2 was covered with a layer of particulate matter, and the agglomerates of titanium dioxide particles were clearly seen in the corresponding magnified pictures. No particles were observed in the SEM pictures of the examples, which also indicates that the titanium dioxide in the examples has a higher dispersibility than in comparative example 2.
Comparison of adsorption performance: the adsorption performance of comparative example 2 and examples on cationic dyes was examined under neutral conditions with a methylene blue solution at an initial concentration of 10 mg/L. As can be seen from FIG. 3, the adsorption time of the methylene blue in the examples reaches 30 minutes to reach saturation, the adsorption amount reaches 23.4mg/g, the removal rate of the methylene blue reaches 96.8%, and the solution after adsorption is colorless and transparent. While the adsorption capacity of the comparative example 1 and the comparative example 2 to methylene blue is much lower than that of the examples, namely 3.0mg/g and 2.5mg/g, the solution still has dark blue after adsorption. The possible reason why the examples have far higher adsorption performance than the comparative examples is that amorphous titanium dioxide therein remains rich in polar functional groups, and the in-situ preparation method ensures a high specific surface area of titanium dioxide, and thus can adsorb more organic dyes.
And (3) comparing the degradation performance: the degradation performance of organic dyes in comparative example 2 and the examples was examined under ultraviolet light conditions with an initial concentration of 10mg/L of rhodamine B solution (FIG. 4). At the initial stage of degradation, comparative example 2 had a faster degradation rate and the kinetics also followed the first order kinetics of photocatalytic degradation, but as degradation proceeded, the examples showed accelerated degradation of rhodamine B, and finally both were able to achieve 95% removal in 70 minutes. In the repeated degradation experiment of fig. 5, the example can maintain a high degradation rate after one degradation, and the removal rate of five degradations is higher than 93%, so the example is more advantageous in repeated use. Through characterization of ultraviolet-visible diffuse reflection of samples in comparative example 2, example and example 2 (fig. 6), it can be clearly understood that the band gap width of example 2 is about 2.4eV, and energy level transition can occur to generate radicals to degrade organic pollutants in response to visible light; while comparative example 2 and example 1 both have a band gap width greater than 2.9eV and are not capable of contaminant degradation using visible light. The degradation performance of example 2 and comparative example 2 was examined under simulated sunlight with a tetracycline solution of 20mg/L as an initial concentration (FIG. 7), and the removal rates of tetracycline at 120 minutes were 83% and 25%, respectively. Influence of preparation conditions on microsphere morphology: as can be seen from tables 1 and 2, as the amount of n-butyl titanate prehydrolysis liquid added was increased, the cellulose concentration was increased, the liquid paraffin/water volume ratio was increased, the amount of span 80 added was increased, the stirring speed was increased, and the reaction temperature was increased, the microsphere size was decreased. Wherein the addition amount of the n-butyl titanate and the titanium dioxide loading amount in the microspheres show good linear correlation. And with the increase of the titanium dioxide loading capacity, the adsorption performance and the degradation performance of the microspheres are increased.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (8)
1. A method for preparing titanium dioxide/cellulose nano composite microspheres in situ is characterized by comprising the following steps:
(1) preparing prehydrolysis liquid of n-butyl titanate: mixing n-butyl titanate and triethanolamine at room temperature, dropwise adding deionized water into the mixed solution, and reacting to obtain prehydrolysis liquid;
(2) preparing a gel prefabricated liquid: dissolving lithium hydroxide and urea by using deionized water, and freezing; adding the dried cellulose into the frozen mixed solvent, and adding the n-butyl titanate prehydrolysis liquid obtained in the step (1) under the stirring condition to obtain a stable n-butyl titanate prehydrolysis liquid/cellulose mixed solution;
(3) preparing titanium dioxide/cellulose microspheres: adding span 80 serving as a surfactant into liquid paraffin, uniformly stirring, adding the gel prefabricated liquid obtained in the step (2), stirring to obtain a water-in-oil emulsion, and gelatinizing the emulsion at room temperature to obtain the titanium dioxide/cellulose microspheres.
2. The method for preparing the titanium dioxide/cellulose nano composite microspheres in situ according to claim 1, wherein in the step (1), the molar ratio of n-butyl titanate to triethanolamine is 0.01 to 10.0; the concentration of n-butyl titanate is 0.1mol/L to 5 mol/L.
3. The method for preparing titanium dioxide/cellulose nano composite microspheres in situ according to claim 1, wherein in the step (1), deionized water can be replaced by a metal cation (iron ions, silver ions and the like) solution or a non-metal anion (sodium lignosulfonate, humic acid and the like) solution; in the step (2), the cellulose dissolving system can also be a sodium hydroxide/urea/thiourea system, a sodium hydroxide/lithium chloride/urea system or a sodium hydroxide/urea system;
in the step (2), the cellulose may be native cellulose, bacterial cellulose, microcrystalline cellulose, nanocellulose (cellulose nanocrystal and cellulose nanofiber), and water-soluble diffraction cellulose (carboxymethyl cellulose).
4. The method for preparing the titanium dioxide/cellulose nano composite microspheres in situ according to claim 1, wherein in the step (2), the mass fraction of the cellulose in the solution is 0.01-10 wt%; in the step (2), the mass ratio of the n-butyl titanate prehydrolysis liquid to the cellulose solution is as follows: 0.01 to 0.5; in the step (3), the volume ratio of the liquid paraffin to the gel prefabricated liquid is as follows: 1-100; in the step (3), the mass-to-volume ratio of span 80 to the emulsion is as follows: 0.01 to 0.5.
5. The method for preparing titanium dioxide/cellulose nano composite microspheres in situ according to claim 1, wherein in the step (3), the stirring manner of the emulsion preparation is mechanical stirring or stirring by using an emulsion homogenizer, and the rotation speed is 300-30000 rpm.
6. The modification method for in-situ preparation of titanium dioxide/cellulose nano-composite microspheres according to claim 1, wherein in the step (3), the temperature for gelation of the emulsion is 0-80 ℃.
7. The method of preparing the titanium dioxide/cellulose nanocomposite microsphere according to claim 1, wherein the method comprises the following steps:
(1) preparing a rhodamine B solution: weighing a certain amount of rhodamine B, dissolving the rhodamine B with deionized water, and fixing the volume for later use;
(2) degrading an intermediate modified microsphere by using rhodamine B: adding the microspheres in the claim 1 into a rhodamine B solution, adding a certain amount of hydrogen peroxide, degrading the rhodamine B under the illumination condition, and obtaining the modified microspheres through settling separation after the solution is colorless and transparent.
8. Use of the composite microspheres of claim 1 and the modified microspheres of claim 7 in wastewater treatment.
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