CN113368904A - Preparation method of nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier - Google Patents
Preparation method of nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier Download PDFInfo
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 100
- 229920001577 copolymer Polymers 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 239000007787 solid Substances 0.000 claims abstract description 119
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000008367 deionised water Substances 0.000 claims abstract description 86
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 86
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 78
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 76
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 72
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 69
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000005406 washing Methods 0.000 claims abstract description 59
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- 238000001035 drying Methods 0.000 claims abstract description 45
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 30
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 30
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 28
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000000967 suction filtration Methods 0.000 claims abstract description 18
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims abstract description 16
- 229910052722 tritium Inorganic materials 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 95
- 239000012043 crude product Substances 0.000 claims description 46
- 239000002270 dispersing agent Substances 0.000 claims description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- 229920002554 vinyl polymer Polymers 0.000 claims description 34
- 229920000620 organic polymer Polymers 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 18
- 238000012216 screening Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 15
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 6
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 claims description 6
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000002351 wastewater Substances 0.000 abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 85
- 239000000178 monomer Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical class C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- -1 HPMA modified nano titanium dioxide Chemical class 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B01J35/30—
-
- B01J35/51—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
Abstract
The invention discloses a preparation method of a nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier, which is characterized by mainly comprising the following steps: mixing and heating solvents N, N-dimethylformamide, nano titanium dioxide and hydroxypropyl methacrylate for reaction, and then carrying out suction filtration, washing and drying to obtain modified nano titanium dioxide; adding deionized water, organic matters and a surfactant into a reactor, heating while stirring, adding a mixture of mixed styrene, divinylbenzene, modified nano titanium dioxide, toluene, benzoyl peroxide, n-heptane and dichloroethane, heating for suspension polymerization reaction, and filtering to obtain a solid; and (3) washing, extracting, filtering, washing and drying the solid to obtain the carrier. The carrier has the characteristics of super-hydrophobicity, high compressive strength, large particle size and the like, is suitable for preparing a hydrophobic catalyst, and is used for treating tritium-containing wastewater.
Description
Technical Field
The invention belongs to the preparation of organic high molecular compounds, and relates to a preparation method of a nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier. The nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier prepared by the invention can be used for engineering application of a hydrogen water liquid phase exchange process (called LPCE for short), and is particularly suitable for preparing a metal-loaded catalyst in tritium-containing wastewater treatment (tritium is extracted by heavy water, and tritium is removed by wastewater).
Background
With the increasing number of nuclear facilities put into operation, the tritiated water produced by them is also growing substantially. Data show that about ten thousand tons of tritium-containing wastewater and tritium-containing heavy water are generated in China every year, and a healthy disposal library does not exist at present for high-radioactive substances in the spent fuel. Tritium is a valuable strategic resource as a high-radiation harmful substance and has great value which cannot be ignored. Therefore, tritium removal treatment and purification of high-concentration tritium-containing wastewater become inevitable options for future development. From the economic and safety aspects, the tritium in the tritium-containing water (heavy water) is treated by a hydrogen isotope catalytic exchange reaction (abbreviated as LPCE), and a traditional inorganic hydrophilic catalyst, such as platinum/aluminum oxide (Pt/A1)2O3) When applied to hydrogen-water catalytic exchange reaction, the catalyst is easy to generate poisoning when encountering liquid water,Deactivation, etc. the hydrophobic catalyst can speed the hydrogen isotope catalytic reaction, so that the hydrophobic catalyst is the key material for completing the hydrogen-water liquid phase catalytic exchange. In the prior art, the mainstream hydrophobic catalyst Pt/SDB (SDB is short for styrene-divinylbenzene copolymer) has become a kind of important research and application. The existing preparation method has the following defects and shortcomings: the SDB hydrophobic catalyst carrier has poor hydrophobic stability, insufficient pressure resistance, short service life, easy loss of active components, failure of meeting engineering requirements and the like; it is necessary to investigate the doping modification of SDB hydrophobic catalyst supports. Nano titanium dioxide (nano-TiO)2) Has the characteristics of high hardness, high melting point and the like; unmodified nano-TiO2The surface energy is high, and the oil phase is difficult to uniformly disperse in the oil phase and directly enters the oil phase to realize suspension polymerization doping; therefore, it is necessary to perform surface modification using a silane coupling agent KH570, an interfacial compatibilizer, hydroxypropyl methacrylate (HPMA), or the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier. The invention provides a preparation method of a nano titanium dioxide hybrid modified (doped) styrene-divinylbenzene copolymer catalyst carrier for ternary polymerization, and the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier which has super hydrophobicity, high compressive strength, large particle size and controllable pore structure and can provide a loaded active site.
The content of the invention is as follows: the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is characterized by comprising the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Taking 80-100 parts by mass of N, N-dimethylformamide (DMF for short), adding 5-10 parts by mass of nano titanium dioxide and 4-20 parts by mass of hydroxypropyl methacrylate (HPMA for short), mixing, heating to 90-100 ℃, reacting for 1.5-3 hours, and then performing suction filtration, washing with ethanol and deionized water, and drying to obtain modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 200-400 parts by mass of deionized water, 1-6 parts by mass of an organic polymer dispersant, 0.1-0.6 part by mass of a surfactant, 2-10 parts by mass of styrene, 2-10 parts by mass of divinylbenzene, 1-16 parts by mass of toluene, 0.1-0.6 part by mass (preferably 0.1-0.5 part by mass) of benzoyl peroxide, 12-24 parts by mass of n-heptane, 5-12 parts by mass of dichloroethane, and modified nano titanium dioxide (i.e., HPMA-TiO)2) Taking raw materials of each component in a mass ratio of 0.1-2 parts by mass;
adding deionized water, an organic polymer dispersant and a surfactant into a reactor, heating to 40-70 ℃ under stirring, adding a mixture of mixed styrene, divinylbenzene, modified nano-titanium dioxide, toluene (serving as a pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into the reactor after a solid is dissolved, heating to 80-95 ℃, carrying out suspension polymerization reaction under (continuous) stirring, reacting for 7-9 h, and filtering to obtain a solid, namely a crude product (called HPMA-TiO) of the nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer2Crude product of SDB);
the organic polymer dispersant is any one of polyvinyl alcohol-1788, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, hydroxyethyl cellulose, gelatin and sodium carboxymethyl cellulose;
the surfactant is any one of sodium stearate, sodium dodecyl benzene sulfonate and sodium octadecyl sulfate;
c. preparation of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst support):
d, sequentially using deionized water and water to remove the solid obtained in the step bWashing with water and ethanol; extracting the solid in a Soxhlet extractor (equipment production providing enterprises are Hangzhou Feicheng instruments Co., Ltd.) for 12-48 h (at the temperature of 20-30 ℃) by using acetone with the mass being 3-8 times that of the solid, filtering, and washing the solid with absolute ethyl alcohol and deionized water in sequence to obtain the porous globular solid; drying the porous and globular solid (drying at 50-60 deg.C under 0.1MPa for 12-36 hr), sieving (taking out HPMA-TiO with particle size of 2-4 mm2SDB catalyst carrier), namely the hydrophobic catalyst carrier (HPMA-TiO for short) of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer is prepared2/SDB catalyst support).
The invention comprises the following steps: step a, preparing modified nano titanium dioxide (HPMA-TiO for short)2) Can be replaced by:
heating 80-100 parts by mass of N, N-dimethylformamide (DMF for short) serving as a solvent to 65-72 ℃, adding 5-10 parts by mass of nano titanium dioxide and 4-20 parts by mass of hydroxypropyl methacrylate (HPMA for short) for mixing, heating to 90-100 ℃, reacting for 1.5-3 hours, and then performing suction filtration, washing with ethanol and deionized water, and drying to obtain the modified nano titanium dioxide.
The invention comprises the following steps: in the step b, the styrene, the divinylbenzene and the modified nano titanium dioxide (HPMA-TiO for short)2) The mass ratio of the amount of (b) is preferably 10:10: 2.
The invention comprises the following steps: the drying in the step a can be drying for 1-3 hours at the temperature of 65-70 ℃.
The invention comprises the following steps: the suspension polymerization reaction is carried out under the stirring in the step b, and preferably, the suspension polymerization reaction is carried out under the condition that the rotation speed of the stirrer is 60 to 280rpm (revolutions per minute) (the rotation speed of the stirrer is preferably 70 to 125 rpm).
The invention comprises the following steps: and c, washing the solid with deionized water and absolute ethyl alcohol in sequence, preferably washing the solid with deionized water and absolute ethyl alcohol for 2-4 times in sequence, wherein the mass of the deionized water and the absolute ethyl alcohol for each washing is 3-8 times of that of the solid.
The invention comprises the following steps: and c, washing the solid with absolute ethyl alcohol and deionized water in sequence, preferably washing the solid with absolute ethyl alcohol and deionized water for 2-4 times in sequence, wherein the mass of the absolute ethyl alcohol and the deionized water for each washing is 3-8 times of that of the solid.
The invention comprises the following steps: and c, drying and screening, preferably drying the solid for 12-36 hours at the temperature of 50-60 ℃ and under the pressure of 0.08MPa, and then screening.
The invention comprises the following steps: the prepared nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst carrier) is used for carrying out adsorption with active components (VIII group metal) and is used for preparing metal-loaded catalysts in tritium-containing wastewater treatment.
The invention comprises the following steps: the used raw materials of each component can be refined firstly: commercially available (from alatin or mcelin) styrene (abbreviated St) was purified by distillation prior to use in the following steps: 500mL of styrene monomer was added to a 1000mL separatory funnel and washed three times with 150mL of 5% NaOH aqueous solution; ② washing with deionized water for many times until the pH value is neutral (7-8), adding a little anhydrous MgSO4Drying after the liquid is clear; thirdly, decompressing and rectifying the dried styrene, and collecting the distilled fraction for later use. The distillation process of divinyl benzene (DVB for short), tert-butyl styrene (t-Bu for short) and methyl methacrylate (MMA for short) monomers is the same as that of styrene monomers. Benzoyl peroxide (BPO for short) adopts chloroform as solvent and CH3OH as a precipitant, and recrystallization refining.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the invention adopts styrene as monomer, modified nano titanium dioxide as modified functional monomer, divinyl benzene as cross-linking agent, benzoyl peroxide as initiator, n-heptane as pore-forming agent and dichloroethane as solubilizerThe organic polymer dispersant (polyvinyl alcohol-1788, etc.) is an organic polymer dispersant, sodium dodecyl benzene sulfonate is a surfactant, the double bond in the introduced functional monomer HPMA is utilized to play a powerful gain to Pt load, a better load effect is played to a catalytic active component, the loss of the active component is reduced, and the monomer has a longer molecular chain, so that a hydrophobic layer can be formed on the surface of the nano titanium dioxide, and the hydrophobicity of a modified carrier is increased; in addition, the introduced modified inorganic nanoparticles have excellent mechanical properties, and the compression resistance and hydrophobicity of the SDB are greatly improved; under the condition, the porous HPMA-TiO with super hydrophobicity, high compressive strength and active functional groups can be prepared2SDB hydrophobic catalyst carrier, the reaction system used in the method has the capacity of enlarging production;
(2) according to the invention, the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is prepared by suspension polymerization and ternary polymerization; the suspension polymerization is essentially a polymerization reaction initiated by an oil-soluble initiator by dispersing a monomer into numerous small liquid beads and suspending the beads in water with strong agitation by the action of a dispersant. The polymerization system is composed of hydrophobic monomer, disperse phase, stabilizer and oil phase initiator. In order to make the resulting resin have a porous structure, a porogen needs to be added to the monomer. The loading effect of the active component is improved by introducing functional groups and double bonds; in order to improve the hydrophobicity, a monomer with strong hydrophobicity and rigidity is added for improvement; in order to reduce the water solubility of the added monomer and avoid uneven adhesion of oil droplets; styrene, divinylbenzene and HPMA modified nano titanium dioxide are taken as ternary polymerization monomers, an initiator is dissolved in the monomers, and then the monomers are mixed with a pore-foaming agent to form an oily mixture (oil phase); dispersing the oil phase into liquid drops in the water phase through the shearing force generated during stirring; under the selected temperature and pressure conditions, the reactivity ratios of the reaction monomers are all less than 1, and the reaction monomers are all prone to copolymerization; the bead shape is formed by the interfacial tension existing between the oil phase and the water phase, and the uniform particles are obtained under the condition that the stirring speed is properly controlled and the water phase dispersion stabilizer is used; with the progress of the reaction, different molecular chains are continuously crosslinked with each other to gradually form a three-dimensional network structure, and after reaching a certain degree, a polymer chain cannot be dissolved and separated out in an oil phase to generate phase separation; the polymer is now in one phase (solid phase) and the remaining monomer and porogen are in the other phase (liquid phase); the reaction is continued, the solid phase is continuously increased, the liquid phase is continuously reduced, after the reaction is finished, a spherical solid polymer is formed, and the pore-forming agent is dispersed in the sphere; then using solvent washing or extracting method to remove pore-forming agent, the space occupied by original pore-forming agent is the pores in the ball, these pores are mutually communicated, so that the adsorption resin possesses larger specific surface and pore volume; inorganic nano particles introduced by a ternary comonomer enable the obtained resin to have high pressure-resistant super-hydrophobic performance, so that a nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is obtained;
(3) the suspension polymerization method adopted by the invention has the characteristics of simplicity, convenience and feasibility, and can be used for proportioning and feeding at one time; compared with a single dispersant, the organic polymer dispersant and the sodium dodecyl benzene sulfonate have better dispersing effect and are easy to stabilize and homogenize oil droplets; the preparation method has the advantages that the suspension polymerization ternary copolymerization is realized by selecting a modified monomer with a proper reactivity ratio, a carrier with a large specific surface area and a proper pore size and pore volume is synthesized, and the carrier shows a hydrophobic angle of 140-153 degrees and a compressive strength of 80-120N under the test of a static water contact angle and a universal tester tensile machine;
(4) the prepared nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier has higher loading stability on active components, improves the catalytic performance of the catalyst, has the advantages of reducing mass transfer resistance of a bed layer, preventing flooding, improving fluid exchange efficiency and the like, is used for engineering applications such as heavy water tritium extraction and wastewater tritium removal, is high in catalytic efficiency, excellent in hydrophobic stability, can be used at normal temperature, and has a good use effect;
(5) the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is a spherical pellet, has larger specific surface area and pore diameter, and is rich in coordination functional groups such as carbonyl, residual double bonds and the like; the modified nano titanium dioxide is prepared by reacting and suspending styrene and divinylbenzene in one pot, and has simple preparation and low cost; the adsorption capacity to cobalt ions is strong, and the capacity is high; the composite material has super-hydrophobicity, a hydrophobic angle of 140-153 degrees, high compressive strength (the compressive strength reaches 80-120N), large particle size (the diameter reaches 2-4 mm), controllable pore structure and capability of providing a load active site; simple process, easy operation and strong practicability.
Thereby providing.
The invention aims to overcome the defects of the prior art and provides a preparation method of a nano titanium dioxide doped styrene-divinylbenzene copolymer catalyst carrier. The preparation method of the hydrophobic catalyst carrier of the nanometer titanium dioxide doped styrene-divinylbenzene copolymer.
The invention belongs to the preparation of organic high molecular compounds, and relates to a preparation method of a nano titanium dioxide doped styrene-divinylbenzene copolymer catalyst carrier. The nano titanium dioxide doped styrene-divinylbenzene copolymer catalyst carrier prepared by the method has the advantages of strong load performance, less Pt loss, improved catalytic performance, improved fluid exchange efficiency and the like on noble metal Pt in the preparation aspect of Pt/SDB hydrophobic catalysts (hydrophobic angle is 140-153 degrees, compressive strength is 80-120N), and is particularly suitable for engineering application of hydrogen water liquid phase exchange process (LPCE).
Drawings
FIG. 1 shows a hydrophobic catalyst support (HPMA-TiO for short) of a nano-titania hybrid modified styrene-divinylbenzene copolymer prepared according to the present invention (example 3)2SDB catalyst support); the IR spectrogram shows that the catalyst carrier has rich benzene ring structure, hydroxyl, ether bond and other functional groups;
FIG. 2 shows HPMA-TiO prepared according to the invention (example 3)2Thermal analysis curve of SDB catalyst carrier; the thermal analysis curve shows that the catalyst carrier has better thermal stability, and the initial thermal decomposition temperature reaches 385.68 ℃;
FIG. 3 shows HPMA-TiO prepared according to the invention (example 3)2The hydrophobic angle test of the SDB catalyst support with SDB; the static water contact angle test shows that the HPMA-TiO2The hydrophobic angle of the/SDB carrier reaches 152.17 degrees, so that super-hydrophobicity is achieved;
FIG. 4 shows HPMA-TiO prepared according to the invention (example 3)2Scanning electron micrographs of/SDB catalyst support; scanning electron microscope finds the HPMA-TiO2the/SDB carrier has a porous structure, good sphericity and smooth surface;
FIG. 5 shows HPMA-TiO prepared according to the invention (example 3)2X-ray diffraction curves of/SDB catalyst support and SDB; because the added nano titanium dioxide is in anatase type, HPMA-TiO is caused by less added nano titanium dioxide2The X-ray diffraction curve of the/SDB is a steamed bun peak when 2 theta = 10-20 degrees, and a sharp peak appears when 2 theta =25 degrees;
FIG. 6 shows HPMA-TiO prepared according to the invention (example 3)2A Lagrange pseudo first-order linear fitting graph of the SDB catalyst carrier; the figure illustrates that the fitting correlation coefficient reaches 0.78529, which indicates that the adsorption process is relatively in accordance with the Lagrangian pseudo-first-order equation, but the Qe calculated by the equation is too different from the Qe of an actual experiment, so that a small part of the adsorption process is physically adsorbed;
FIG. 7 shows HPMA-TiO prepared according to the invention (example 3)2A Lagrangian pseudo-second-order linear fitting graph of the SDB catalyst carrier; the figure illustrates that the fitting correlation coefficient reaches 0.9995, which indicates that the adsorption process is relatively in accordance with a Lagrangian pseudo-second-order equation, but the Qe calculated by the equation is almost the same as the Qe of an actual experiment, so that the adsorption process mainly generates chemical adsorption;
FIG. 8 shows HPMA-TiO prepared according to the invention (example 3)2Fitting graph of an intra-particle diffusion model of the SDB catalyst carrier; the figure illustrates that the fitted correlation coefficient reached 0.73194, indicating that the adsorption process is less consistent with the intra-particle diffusion model, and that the fitted straight line does not pass through the origin, indicating that the speed control step in the adsorption process is not a particle diffusion step;
FIG. 9 shows HPMA-TiO prepared according to the invention (example 3)2Langmuir adsorption isotherm fitting of/SDB catalyst supportsA drawing; the figure illustrates that fitting the correlation coefficient to 0.98837, the adsorption process is relatively consistent with the isotherm model;
FIG. 10 shows HPMA-TiO prepared according to the invention (example 3)2A Freude adsorption isotherm fitting graph of the SDB catalyst carrier; the figure illustrates that the combined correlation coefficient reaches 0.98772, and the adsorption process is more consistent with a Freudesy adsorption isotherm model. And 1/n < 1, indicating preferential adsorption.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Example 1:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Taking 80g of N, N-dimethylformamide (DMF for short), adding 5g of nano titanium dioxide and 4g of hydroxypropyl methacrylate (HPMA for short) for mixing, heating to 90 ℃, reacting for 1.5 hours, then carrying out suction filtration, washing with ethanol and deionized water, and drying at 65 ℃ for 1 hour to prepare modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 200g of deionized water, 20992 g of organic polymer dispersant polyvinyl alcohol-20992 g, 0.12g of surfactant sodium dodecyl benzene sulfonate, 5g of styrene, 5g of divinylbenzene, 10g of toluene, 0.1g of benzoyl peroxide, 12g of n-heptane, 5g of dichloroethane and modified nano titanium dioxide (namely HPMA-TiO)2) Taking raw materials of each component according to a mass ratio of 0.5 g;
adding deionized water, organic polymer dispersant and surfactant into a reactor, stirring, and heating to 40 deg.CAfter the solid is dissolved, adding the mixture of the mixed styrene, the divinylbenzene, the modified nano titanium dioxide, the toluene (used as a pore-foaming agent), the benzoyl peroxide, the n-heptane and the dichloroethane into a reactor, heating to 80 ℃, carrying out suspension polymerization reaction under (continuous) stirring, after the reaction time is 7 hours, filtering to obtain the solid, namely the crude product (HPMA-TiO) of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer2Crude product of SDB);
c. preparation of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor for 12 hours by using acetone with the mass of 3 times of that of the solid, filtering, and washing the solid with absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2/SDB catalyst support).
In this example 1, the hydrophobic angle of the modified nano titania obtained in step a is 123.4 °, which is greatly improved compared to the hydrophobic property of the nano titania in a hydrophilic state; the hydrophobic catalyst carrier prepared in the embodiment 1 has a hydrophobic angle of 144.12 degrees, a compressive strength of 97.2N and a particle size of about 2-3 mm.
Example 2:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Taking 90g of N, N-dimethylformamide (DMF for short), adding 6g of nano titanium dioxide and 5g of hydroxypropyl methacrylate (HPMA for short) for mixing, heating to 95 ℃, reacting for 1.5 hours, then carrying out suction filtration, washing with ethanol and deionized water, and drying at 65 ℃ for 1 hour to prepare modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 200g of deionized water, 20991 g of organic polymer dispersant polyvinyl alcohol, 0.5g of surfactant sodium dodecyl benzene sulfonate, 7g of styrene, 10g of divinyl benzene, 9g of toluene, 0.3g of benzoyl peroxide, 12g of n-heptane, 5g of dichloroethane and modified nano titanium dioxide (namely HPMA-TiO)2) Taking raw materials of each component according to a mass ratio of 0.5 g;
adding deionized water, organic polymer dispersant and surfactant into a reactor, heating to 55 ℃ under stirring, adding a mixture of mixed styrene, divinyl benzene, modified nano titanium dioxide, toluene (serving as a pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into the reactor after a solid is dissolved, heating to 82 ℃, carrying out suspension polymerization reaction under (continuous) stirring, reacting for 8 hours, and filtering to obtain a solid, namely a crude product (HPMA-TiO) of the nano titanium dioxide hybrid modified styrene-divinyl benzene copolymer2Crude product of SDB);
c. preparation of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor for 13 hours by using acetone with the mass 6 times that of the solid, filtering, and washing the solid with absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2/SDB catalyst support).
In this embodiment 2, the hydrophobic angle of the modified nano titania obtained in step a is 125.14 °, which is greatly improved compared with the hydrophobic property of the nano titania in a hydrophilic state; the hydrophobic catalyst carrier prepared in the example 1 has a hydrophobic angle of 147.35 degrees, a compressive strength of 96.8N and a particle size of about 2 mm.
Example 3:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Taking 100g of N, N-dimethylformamide (DMF for short), adding 5g of nano titanium dioxide and 5g of hydroxypropyl methacrylate (HPMA for short) for mixing, heating to 90 ℃, reacting for 1.5 hours, then carrying out suction filtration, washing with ethanol and deionized water, and drying at 65 ℃ for 1 hour to prepare modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 300g of deionized water, 17886 g of organic polymer dispersant polyvinyl alcohol, 0.6g of surfactant sodium dodecyl benzene sulfonate, 7g of styrene, 10g of divinyl benzene, 15g of toluene, 0.5g of benzoyl peroxide, 13g of n-heptane, 6g of dichloroethane and modified nano titanium dioxide (namely HPMA-TiO)2) Taking raw materials of each component according to a mass ratio of 0.5 g;
adding deionized water, organic polymer dispersant and surfactant into a reactor, heating to 60 ℃ under stirring, adding a mixture of mixed styrene, divinyl benzene, modified nano titanium dioxide, toluene (serving as a pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into the reactor after a solid is dissolved, heating to 85 ℃, carrying out suspension polymerization reaction under (continuous) stirring, reacting for 9 hours, and filtering to obtain a solid, namely a crude product (HPMA-TiO) of the nano titanium dioxide hybrid modified styrene-divinyl benzene copolymer2Crude product of SDB);
c. preparation of nano-titanium dioxide hybrid modified styreneHydrophobic catalyst support of divinylbenzene copolymer (HPMA-TiO for short)2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor for 24 hours by using acetone with the mass 6 times that of the solid, filtering, and washing the solid with absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2/SDB catalyst support).
In this embodiment 3, the hydrophobic angle of the modified nano titania obtained in step a is 139.75 °, which is greatly improved compared with the hydrophobic property of the nano titania in a hydrophilic state; the hydrophobic catalyst carrier prepared in the example 1 has a hydrophobic angle of 152.17 degrees, compressive strength of 114.42N and a particle size of about 3 mm.
Example 4:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Taking 90g of N, N-dimethylformamide (DMF for short), adding 8g of nano titanium dioxide and 9g of hydroxypropyl methacrylate (HPMA for short) for mixing, heating to 90 ℃, reacting for 2 hours, then carrying out suction filtration, washing with ethanol and deionized water, and drying at 65 ℃ for 2 hours to obtain modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 400g of deionized water, 17996 g of organic polymer dispersant polyvinyl alcohol, 0.3g of surfactant sodium dodecyl benzene sulfonate, 9g of styrene, 10g of divinyl benzene, 16g of toluene, 0.3g of benzoyl peroxide, 15g of n-heptane, 6g of dichloroethane and modified nano titanium dioxide (namely HPMA-TiO)2) Taking raw materials of each component according to a mass ratio of 1.0 g;
adding deionized water, organic polymer dispersant and surfactant into a reactor, heating to 65 ℃ under stirring, adding a mixture of mixed styrene, divinyl benzene, modified nano titanium dioxide, toluene (serving as a pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into the reactor after a solid is dissolved, heating to 90 ℃, carrying out suspension polymerization reaction under (continuous) stirring, and filtering after 9 hours to obtain a solid, namely a crude product (HPMA-TiO) of the nano titanium dioxide hybrid modified styrene-divinyl benzene copolymer2Crude product of SDB);
c. preparation of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor for 36 hours by using acetone with the mass 7 times that of the solid, filtering, and washing the solid with absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2/SDB catalyst support).
In this embodiment 4, the hydrophobic angle of the modified nano titania obtained in step a is 131.2 °, which is greatly improved compared with the hydrophobic property of the nano titania in a hydrophilic state; the hydrophobic catalyst carrier prepared in the embodiment 1 has a hydrophobic angle of 149.12 degrees, a compressive strength of 99.24N and a particle size of about 2.5 mm.
Example 5:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Heating 100g of N, N-Dimethylformamide (DMF) serving as a solvent to 70 ℃, adding 10g of nano titanium dioxide and 20g of hydroxypropyl methacrylate (HPMA) for mixing, heating to 90 ℃, reacting for 2 hours, performing suction filtration, washing with ethanol and deionized water, and drying at 65 ℃ for 1 hour to obtain modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 400g of deionized water, 20994 g of organic polymer dispersant polyvinyl alcohol-20994 g, 0.2g of surfactant sodium dodecyl benzene sulfonate, 10g of styrene, 10g of divinyl benzene, 16g of toluene, 0.1g of benzoyl peroxide, 12g of n-heptane, 5g of dichloroethane and modified nano titanium dioxide (namely HPMA-TiO)2) Taking raw materials of each component according to a mass ratio of 0.5 g;
adding deionized water, organic polymer dispersant and surfactant into a reactor, heating to 70 ℃ under stirring, adding a mixture of mixed styrene, divinyl benzene, modified nano titanium dioxide, toluene (serving as a pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into the reactor after a solid is dissolved, heating to 95 ℃, carrying out suspension polymerization reaction under (continuous) stirring, reacting for 9 hours, and filtering to obtain a solid, namely a crude product (HPMA-TiO) of the nano titanium dioxide hybrid modified styrene-divinyl benzene copolymer2Crude product of SDB);
c. preparation of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor for 12 hours by using acetone with the mass of 8 times of that of the solid, filtering, and washing the solid with absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier(HPMA-TiO for short)2/SDB catalyst support).
In this example 5, the hydrophobic angle of the modified nano titania obtained in step a is 135.47 °, which is greatly improved compared with the hydrophobic property of the nano titania in a hydrophilic state; the hydrophobic catalyst carrier prepared in the example 1 has a hydrophobic angle of 148.31 degrees, compressive strength of 124.57N and a particle size of about 3 mm.
Example 6:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Taking 90 parts by mass of N, N-dimethylformamide (DMF for short) as a solvent, adding 8 parts by mass of nano titanium dioxide and 10 parts by mass of hydroxypropyl methacrylate (HPMA for short) for mixing, heating to 95 ℃ for reaction for 2 hours, and then carrying out suction filtration, washing with ethanol and deionized water and drying to obtain modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 300 parts of deionized water, 300 parts of organic polymer dispersant polyvinyl alcohol-17884 parts by mass, 0.3 part of surfactant sodium dodecyl benzene sulfonate, 10 parts of styrene, 10 parts of divinylbenzene, 9 parts of toluene, 0.3 part of benzoyl peroxide, 16 parts of n-heptane, 8 parts of dichloroethane and modified nano titanium dioxide (namely HPMA-TiO)2) 2 parts by mass of raw materials of each component are taken;
adding deionized water, organic polymer dispersant and surfactant into a reactor, heating to 60 deg.C under stirring, dissolving the solid, adding the mixture of styrene, divinyl benzene, modified nano titanium dioxide, toluene (as pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into the reactor, heating to 90 deg.C, and stirring (continuously)Performing suspension polymerization reaction for 8h, and filtering to obtain solid product (HPMA-TiO) as crude product of nanometer titanium dioxide hybrid modified styrene-divinylbenzene copolymer2Crude product of SDB);
c. preparation of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor (Hangzhou Feichong instruments Co., Ltd.) for 30h by using acetone with the mass 6 times that of the solid, filtering, and washing the solid with absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2/SDB catalyst support).
Example 7:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Taking 80 parts by mass of N, N-dimethylformamide (DMF for short) as a solvent, adding 5 parts by mass of nano titanium dioxide and 4 parts by mass of hydroxypropyl methacrylate (HPMA for short) for mixing, heating to 90 ℃ for reaction for 1.5 hours, and then carrying out suction filtration, washing with ethanol and deionized water and drying to obtain modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 200 parts by mass of deionized water, 1 part by mass of organic polymer dispersant, 0.1 part by mass of surfactant, 2 parts by mass of styrene, 2 parts by mass of divinylbenzene, 1 part by mass of toluene, 0.1 part by mass of benzoyl peroxide, 12 parts by mass of n-heptane, 5 parts by mass of dichloroethane and modified nano titanium dioxide (i.e. HPMA-TiO)2) 0.1 part by mass of raw materials of each component are taken;
adding deionized water, organic polymer dispersant and surfactant into a reactor, heating to 40 ℃ under stirring, adding a mixture of mixed styrene, divinyl benzene, modified nano titanium dioxide, toluene (serving as a pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into the reactor after a solid is dissolved, heating to 80 ℃, carrying out suspension polymerization reaction under (continuous) stirring, reacting for 7 hours, and filtering to obtain a solid, namely a crude product (HPMA-TiO) of the nano titanium dioxide hybrid modified styrene-divinyl benzene copolymer2Crude product of SDB);
the organic polymer dispersant is any one of polyvinyl alcohol-1788, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, hydroxyethyl cellulose, gelatin and sodium carboxymethyl cellulose;
the surfactant is any one of sodium stearate, sodium dodecyl benzene sulfonate and sodium octadecyl sulfate;
c. preparation of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor (Hangzhou Feichong instruments Co., Ltd.) (at the temperature of 20-30 ℃) for 12 hours by using acetone with the mass being 3 times that of the solid, filtering, and washing the solid by using absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2/SDB catalyst support).
Example 8:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparation of modified Nano TitaniaAbbreviated as HPMA-TiO2）：
Taking 100 parts by mass of N, N-dimethylformamide (DMF for short), adding 10 parts by mass of nano titanium dioxide and 20 parts by mass of hydroxypropyl methacrylate (HPMA for short), mixing, heating to 100 ℃, reacting for 3 hours, and then performing suction filtration, washing with ethanol and deionized water, and drying to obtain modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: according to the weight portion, 400 portions of deionized water, 6 portions of organic polymer dispersant, 0.6 portion of surfactant, 10 portions of styrene, 10 portions of divinylbenzene, 16 portions of toluene, 0.6 portion of benzoyl peroxide, 24 portions of n-heptane, 12 portions of dichloroethane and modified nano titanium dioxide (namely HPMA-TiO)2) 2 parts by mass of raw materials of each component are taken;
adding deionized water, organic polymer dispersant and surfactant into a reactor, heating to 70 ℃ under stirring, adding a mixture of mixed styrene, divinyl benzene, modified nano titanium dioxide, toluene (serving as a pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into the reactor after a solid is dissolved, heating to 95 ℃, carrying out suspension polymerization reaction under (continuous) stirring, reacting for 9 hours, and filtering to obtain a solid, namely a crude product (HPMA-TiO) of the nano titanium dioxide hybrid modified styrene-divinyl benzene copolymer2Crude product of SDB);
the organic polymer dispersant is any one of polyvinyl alcohol-1788, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, hydroxyethyl cellulose, gelatin and sodium carboxymethyl cellulose;
the surfactant is any one of sodium stearate, sodium dodecyl benzene sulfonate and sodium octadecyl sulfate;
c. preparation of Nano Titania hybrid modified styrene-Divinylbenzene copolymer hydrophobic catalyst support (simple)Scale HPMA-TiO2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor (Hangzhou Feichong instruments Co., Ltd.) (at the temperature of 20-30 ℃) for 48 hours by using acetone with the mass being 8 times that of the solid, filtering, and washing the solid by using absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2/SDB catalyst support).
Example 9:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Taking 90 parts by mass of N, N-dimethylformamide (DMF for short) as a solvent, adding 7 parts by mass of nano titanium dioxide and 12 parts by mass of hydroxypropyl methacrylate (HPMA for short) for mixing, heating to 95 ℃ for reaction for 2.5 hours, and then carrying out suction filtration, washing with ethanol and deionized water and drying to obtain modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 300 parts by mass of deionized water, 3 parts by mass of organic polymer dispersant, 0.3 part by mass of surfactant, 6 parts by mass of styrene, 6 parts by mass of divinylbenzene, 8 parts by mass of toluene, 0.3 part by mass of benzoyl peroxide, 18 parts by mass of n-heptane, 8 parts by mass of dichloroethane and modified nano titanium dioxide (i.e. HPMA-TiO)2) 1 part by mass of raw materials of each component are taken;
adding deionized water, organic polymer dispersant and surfactant into a reactor, heating to 55 deg.C under stirring, dissolving the solid, and mixing with styrene, divinylbenzene, modified nanometer titanium dioxide and tolueneAdding a mixture of a pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into a reactor, heating to 87 ℃, carrying out suspension polymerization reaction under (continuous) stirring for 8 hours, and filtering to obtain a solid, namely a crude product (HPMA-TiO) of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer2Crude product of SDB);
the organic polymer dispersant is any one of polyvinyl alcohol-1788, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, hydroxyethyl cellulose, gelatin and sodium carboxymethyl cellulose;
the surfactant is any one of sodium stearate, sodium dodecyl benzene sulfonate and sodium octadecyl sulfate;
c. preparation of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor (Hangzhou Feichong instruments Co., Ltd.) (at a temperature of 20-30 ℃) for 30 hours by using acetone with the mass being 5 times that of the solid, filtering, and washing the solid by using absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2/SDB catalyst support).
Example 10:
the preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier comprises the following steps:
a. preparing modified nano titanium dioxide (HPMA-TiO for short)2）：
Taking 92 parts by mass of N, N-dimethylformamide (DMF for short) as a solvent, adding 8 parts by mass of nano titanium dioxide and 13 parts by mass of hydroxypropyl methacrylate (HPMA for short) for mixing, heating to 96 ℃, reacting for 3 hours, and then carrying out suction filtration, washing with ethanol and deionized water, and drying to obtain modified nano titanium dioxide;
b. preparation of crude product of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer (HPMA-TiO for short)2Crude product of SDB):
preparing materials: 320 parts by mass of deionized water, 3.5 parts by mass of organic polymer dispersant, 0.4 part by mass of surfactant, 7 parts by mass of styrene, 7 parts by mass of divinylbenzene, 7 parts by mass of toluene, 0.5 part by mass of benzoyl peroxide, 19 parts by mass of n-heptane, 9 parts by mass of dichloroethane and modified nano titanium dioxide (namely HPMA-TiO)2) 1.2 parts by mass of raw materials of each component;
adding deionized water, organic polymer dispersant and surfactant into a reactor, heating to 60 ℃ under stirring, adding a mixture of mixed styrene, divinyl benzene, modified nano titanium dioxide, toluene (serving as a pore-forming agent), benzoyl peroxide, n-heptane and dichloroethane into the reactor after a solid is dissolved, heating to 89 ℃, carrying out suspension polymerization reaction under (continuous) stirring, reacting for 9 hours, and filtering to obtain a solid, namely a crude product (HPMA-TiO) of the nano titanium dioxide hybrid modified styrene-divinyl benzene copolymer2Crude product of SDB);
the organic polymer dispersant is any one of polyvinyl alcohol-1788, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, hydroxyethyl cellulose, gelatin and sodium carboxymethyl cellulose;
the surfactant is any one of sodium stearate, sodium dodecyl benzene sulfonate and sodium octadecyl sulfate;
c. preparation of nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst support):
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid with acetone 6 times the mass of the solid in Soxhlet extractor (Hangzhou Fei jumping apparatus Co., Ltd.) for 36 hr, filtering, and sequentially extracting the solid with acetoneWashing with absolute ethyl alcohol and deionized water to obtain porous globular solid; drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2/SDB catalyst support).
Example 11:
a preparation method of a nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier, the step a prepares modified nano titanium dioxide (HPMA-TiO for short)2) Replacing the steps as follows: heating 80 parts by mass of N, N-Dimethylformamide (DMF) serving as a solvent to 65 ℃, adding 5 parts by mass of nano titanium dioxide and 4 parts by mass of hydroxypropyl methacrylate (HPMA) for mixing, heating to 90 ℃, reacting for 1.5 hours, and then performing suction filtration, washing with ethanol and deionized water, and drying to obtain modified nano titanium dioxide; the other examples are the same as those in examples 6 to 10, and are omitted.
Example 12:
a preparation method of a nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier, the step a prepares modified nano titanium dioxide (HPMA-TiO for short)2) Replacing the steps as follows: heating 100 parts by mass of N, N-Dimethylformamide (DMF) serving as a solvent to 72 ℃, adding 10 parts by mass of nano titanium dioxide and 20 parts by mass of hydroxypropyl methacrylate (HPMA) for mixing, heating to 100 ℃, reacting for 3 hours, and then performing suction filtration, washing with ethanol and deionized water, and drying to obtain modified nano titanium dioxide; the other examples are the same as those in examples 6 to 10, and are omitted.
Example 13:
a preparation method of a nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier, the step a prepares modified nano titanium dioxide (HPMA-TiO for short)2) Replacing the steps as follows: heating 90 parts by mass of N, N-Dimethylformamide (DMF) as a solvent to 70 ℃, adding 8 parts by mass of nano titanium dioxide and 12 parts by mass of hydroxypropyl methacrylate (HPMA) for mixing, heating to 95 ℃, reacting for 2.5 hours, and then carrying outCarrying out suction filtration, washing with ethanol and deionized water, and drying to obtain modified nano titanium dioxide; the other examples are the same as those in examples 6 to 10, and are omitted.
In examples 6 to 13 above: the drying in the step a can be drying at any temperature of 65-70 ℃ for any time of 1-3 hours.
In examples 6 to 13 above: the suspension polymerization reaction under stirring in the step b is a suspension polymerization reaction under the condition that the rotation speed of the stirrer is any one of 60 to 280rpm (revolutions per minute) (preferably any one of 70 to 125 rpm).
In examples 6 to 13 above: and c, washing the solid with deionized water and absolute ethyl alcohol in sequence, wherein the solid is washed with deionized water and absolute ethyl alcohol for any one of 2-4 times in sequence, and the mass of the deionized water and the absolute ethyl alcohol for each washing is 3-8 times that of the solid.
In examples 6 to 13 above: and c, washing the solid with absolute ethyl alcohol and deionized water in sequence, wherein the solid is washed with the absolute ethyl alcohol and the deionized water for any one of 2-4 times in sequence, and the mass of the absolute ethyl alcohol and the deionized water for each washing is 3-8 times of that of the solid.
In examples 6 to 13 above: in the step c, the drying and screening can be carried out by drying the solid at any temperature of 50-60 ℃ under the pressure of 0.08MPa for any time of 12-36 h and then screening.
In examples 6 to 13 above: the prepared nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier (HPMA-TiO for short)2SDB catalyst carrier) is used for carrying out adsorption with active components (VIII group metal) and is used for preparing metal-loaded catalysts in tritium-containing wastewater treatment.
The content of the invention and the embodiment are as follows: the used raw materials of each component can be refined firstly: commercially available (from alatin or mcelin) styrene (abbreviated St) was purified by distillation prior to use in the following steps: 500mL of styrene monomer was added to a 1000mL separatory funnel using 150mLWashing three times with 5% NaOH aqueous solution; ② washing with deionized water for many times until the pH value is neutral (7-8), adding a little anhydrous MgSO4Drying after the liquid is clear; thirdly, decompressing and rectifying the dried styrene, and collecting the distilled fraction for later use. The distillation process of divinyl benzene (DVB for short), tert-butyl styrene (t-Bu for short) and methyl methacrylate (MMA for short) monomers is the same as that of styrene monomers. Benzoyl peroxide (BPO for short) adopts chloroform as solvent and CH3OH as a precipitant, and recrystallization refining.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the proportions used, not specifically noted, are mass (weight) proportions; the parts by mass may all be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, rotating speed, etc.) and the numerical values of the components in each step are in the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (10)
1. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is characterized by comprising the following steps:
a. preparing modified nano titanium dioxide:
taking 80-100 parts by mass of N, N-dimethylformamide as a solvent, adding 5-10 parts by mass of nano titanium dioxide and 4-20 parts by mass of hydroxypropyl methacrylate, mixing, heating to 90-100 ℃, reacting for 1.5-3 hours, and then performing suction filtration, washing with ethanol and deionized water, and drying to obtain modified nano titanium dioxide;
b. preparation of a crude product of nano-titania hybrid-modified styrene-divinylbenzene copolymer:
preparing materials: taking raw materials of 200-400 parts by mass of deionized water, 1-6 parts by mass of an organic polymer dispersant, 0.1-0.6 part by mass of a surfactant, 2-10 parts by mass of styrene, 2-10 parts by mass of divinylbenzene, 1-16 parts by mass of toluene, 0.1-0.6 part by mass of benzoyl peroxide, 12-24 parts by mass of n-heptane, 5-12 parts by mass of dichloroethane and 0.1-2 parts by mass of modified nano titanium dioxide;
adding deionized water, an organic polymer dispersant and a surfactant into a reactor, heating to 40-70 ℃ under stirring, adding a mixture of mixed styrene, divinylbenzene, modified nano-titanium dioxide, toluene, benzoyl peroxide, n-heptane and dichloroethane into the reactor after a solid is dissolved, heating to 80-95 ℃, carrying out suspension polymerization reaction under stirring for 7-9 h, and filtering to obtain a solid, namely a crude product of the nano-titanium dioxide hybrid modified styrene-divinylbenzene copolymer;
the organic polymer dispersant is any one of polyvinyl alcohol-1788, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2499, polyvinyl alcohol-2699, hydroxyethyl cellulose, gelatin and sodium carboxymethyl cellulose;
the surfactant is any one of sodium stearate, sodium dodecyl benzene sulfonate and sodium octadecyl sulfate;
c. preparing a nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier:
washing the solid obtained in the step b with deionized water and absolute ethyl alcohol in sequence; extracting the solid in a Soxhlet extractor for 12-48 h by using acetone with the mass of 3-8 times that of the solid, filtering, and washing the solid with absolute ethyl alcohol and deionized water in sequence to obtain a porous globular solid; and drying and screening the porous globular solid to obtain the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier.
2. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier as claimed in claim 1, which is characterized in that: replacing the modified nano titanium dioxide prepared in the step a by:
heating 80-100 parts by mass of N, N-dimethylformamide serving as a solvent to 65-72 ℃, adding 5-10 parts by mass of nano titanium dioxide and 4-20 parts by mass of hydroxypropyl methacrylate, mixing, heating to 90-100 ℃, reacting for 1.5-3 hours, and then performing suction filtration, washing with ethanol and deionized water, and drying to obtain the modified nano titanium dioxide.
3. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier as claimed in claim 1, which is characterized in that: in the step b, the mass ratio of the mass parts of the styrene, the divinyl benzene and the modified nano titanium dioxide is 10:10: 2.
4. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier as claimed in claim 2, which is characterized in that: in the step b, the mass ratio of the mass parts of the styrene, the divinyl benzene and the modified nano titanium dioxide is 10:10: 2.
5. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 1, 2, 3 or 4, which is characterized in that: in the step a, the drying is carried out for 1-3 hours at the temperature of 65-70 ℃.
6. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 1, 2, 3 or 4, which is characterized in that: and c, performing suspension polymerization under stirring in the step b, wherein the suspension polymerization is performed under the condition that the rotating speed of the stirrer is 60-280 rpm.
7. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 1, 2, 3 or 4, which is characterized in that: and c, washing the solid with deionized water and absolute ethyl alcohol in sequence, wherein the solid is washed with deionized water and absolute ethyl alcohol for 2-4 times in sequence, and the mass of the deionized water and the absolute ethyl alcohol for each washing is 3-8 times of that of the solid.
8. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 1, 2, 3 or 4, which is characterized in that: and c, washing the solid with absolute ethyl alcohol and deionized water in sequence, wherein the solid is washed with absolute ethyl alcohol and deionized water for 2-4 times in sequence, and the mass of the absolute ethyl alcohol and the deionized water for each washing is 3-8 times of that of the solid.
9. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 1, 2, 3 or 4, which is characterized in that: and c, drying and screening, namely drying the solid for 12-36 hours at the temperature of 50-60 ℃ and under the pressure of 0.08MPa, and then screening.
10. The preparation method of the nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier according to claim 1, 2, 3 or 4, which is characterized in that: the prepared nano titanium dioxide hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier is used for carrying out adsorption with active components and is used for preparing a metal-loaded catalyst in tritium-containing wastewater treatment.
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