CN107973873A - A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier - Google Patents
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier Download PDFInfo
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- CN107973873A CN107973873A CN201711307417.2A CN201711307417A CN107973873A CN 107973873 A CN107973873 A CN 107973873A CN 201711307417 A CN201711307417 A CN 201711307417A CN 107973873 A CN107973873 A CN 107973873A
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- styrene
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- mass parts
- compression
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 114
- 229920001577 copolymer Polymers 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 230000006835 compression Effects 0.000 title claims abstract description 69
- 238000007906 compression Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- JSAIENUMNDAGTD-UHFFFAOYSA-N benzene ethene styrene Chemical compound C1=CC=CC=C1.C=C.C=C.C=CC1=CC=CC=C1 JSAIENUMNDAGTD-UHFFFAOYSA-N 0.000 title claims description 94
- 239000007787 solid Substances 0.000 claims abstract description 133
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 97
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000008367 deionised water Substances 0.000 claims abstract description 78
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000005416 organic matter Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 150000003839 salts Chemical class 0.000 claims abstract description 44
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004094 surface-active agent Substances 0.000 claims abstract description 37
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 34
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 31
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 30
- 235000019400 benzoyl peroxide Nutrition 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
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000012216 screening Methods 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 53
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 53
- 239000012043 crude product Substances 0.000 claims description 39
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- 239000001506 calcium phosphate Substances 0.000 claims description 17
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 17
- 235000011010 calcium phosphates Nutrition 0.000 claims description 17
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 16
- 108010010803 Gelatin Proteins 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 13
- 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 13
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 claims description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 13
- 229920000159 gelatin Polymers 0.000 claims description 13
- 239000008273 gelatin Substances 0.000 claims description 13
- 235000019322 gelatine Nutrition 0.000 claims description 13
- 235000011852 gelatine desserts Nutrition 0.000 claims description 13
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 13
- 239000001095 magnesium carbonate Substances 0.000 claims description 13
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 13
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 13
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 12
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 235000010980 cellulose Nutrition 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 17
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 description 31
- 239000011148 porous material Substances 0.000 description 28
- 239000012535 impurity Substances 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000004088 foaming agent Substances 0.000 description 18
- 239000002270 dispersing agent Substances 0.000 description 16
- 229910001453 nickel ion Inorganic materials 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 14
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 12
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 12
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 10
- 239000012051 hydrophobic carrier Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 7
- 125000002252 acyl group Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052722 tritium Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000003811 acetone extraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011049 pearl Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- -1 Sodium alkyl benzene Chemical class 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011020 pilot scale process Methods 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a kind of preparation method of super-hydrophobic high resistance to compression styrene divinylbenzene copolymer catalyst carrier, it is characterized in that：By deionized water, organic matter, inorganic salts and surfactant are added in reaction vessel, 40~70 DEG C are heated under stirring, the styrene that will have been mixed again, divinylbenzene, methyl methacrylate, t-butyl styrene, benzoyl peroxide, the mixture of normal heptane and dichloroethanes adds, it is heated to 80~95 DEG C, after 7~9h of the lower progress suspension polymerization of stirring, filtering, solids deionized water, absolute ethyl alcohol washs, extracted again with acetone in apparatus,Soxhlet's, then absolute ethyl alcohol is used, deionized water is washed, it is dry, screening, super-hydrophobic high resistance to compression styrene divinylbenzene copolymer catalyst carrier is made.The Pt/SDB hydrophobic catalysts prepared using product of the present invention as carrier, for heavy water detritiation, waste water detritiation, high catalytic efficiency, can room temperature use, using effect is good.
Description
Technical field
The invention belongs to the preparation of organic high molecular compound, is related to a kind of super-hydrophobic high resistance to compression stryrene divinyl base
The preparation method of benzene copolymer catalyst carrier.With super-hydrophobic high resistance to compression (154.8 ° of hydrophobic angle, compression strength produced by the present invention
68.38N) styrene diethylene benzene copoly mer catalyst carrier, in terms of Pt/SDB hydrophobic catalyst preparations, to noble metal
The advantages that there is Pt strong load performance, Pt losses reduction, catalytic performance to improve, and fluid communication efficiency improves, it is particularly suitable
In the engineering application of heavy water detritiation and waste water detritiation etc..
Background technology
Also increase substantially containing surabaya with the increasingly increase of all kinds of nuclear facilities numbers to put into operation, caused by them.
Data show that China there are about the tritium-containing liquid waste of 10,000 tons every year, heavy water containing tritium produces, and for the high radioactivity in spentnuclear fuel
Material, domestic there is presently no sound disposal storehouse.It is also a kind of valuable strategy money while tritium is as high radiation nuisance
Source, has very important substantial worth.Therefore, tritium processing and purification are carried out to high concentration tritium-containing liquid waste becomes following hair
The inevitable choice on Zhan Zhi roads.Consider from economy and secure context, the same position of hydrogen is all employed to the processing containing tritium in surabaya (heavy water)
The method of plain catalyticing exchanging reaction, traditional inorganic hydrophilic catalyst, such as platinum/alundum (Al2O3) (Pt/A12O3), applied to
During hydrogen-water catalyticing exchanging reaction, the problems such as liquid water is easy to produce poisoning, inactivation is run into, and hydrophobic catalyst can be managed more
Accelerate the progress of hydrogen isotope catalytic reaction with thinking, thus hydrophobic catalyst is the crucial material for completing hydrogen-water liquid-phase catalysis exchange
Material.In the prior art, the hydrophobic catalyst Pt/SDB (SDB is the abbreviation of styrene diethylene benzene copoly mer) of mainstream into
The species with applying is studied for emphasis, external scale uses in the industry, and the country is only in pilot scale level.Mainly due to
Existing preparation method exists：SDB hydrophobic catalyst carrier hydrophobic stabilities are poor, the catalytic activity of SDB hydrophobic catalysts deficiency
Poor with catalytic stability, anti-pressure ability deficiency, relatively low with activearm bond strength, service life is short, and active component is easy to run off
The problems such as engineering requires cannot be reached.It is necessary to study the hydrophobic stability of SDB hydrophobic catalyst carriers.
The content of the invention
The purpose of the present invention overcomes the shortcomings of the prior art, there is provided a kind of super-hydrophobic high resistance to compression stryrene divinyl
The preparation method of base benzene copolymer catalyst carrier.The present invention is total to by a kind of super-hydrophobic high resistance to compression styrene-divinylbenzene
The quarternary copolymerized preparation method of polymers catalyst carrier, thus provide it is a kind of have super-hydrophobicity, high compressive strength, big particle diameter,
Pore structure is controllable, and can provide the system of the styrene diethylene benzene copoly mer hydrophobic catalyst carrier in supported active site
Preparation Method.
Present disclosure is：A kind of system of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier
Preparation Method, it is characterized in that step is：
A, dispensing：By 200~400 mass parts of deionized water, 1~6 mass parts of organic matter, 0.01~0.05 mass of inorganic salts
Part, 0.1~0.6 mass parts of surfactant, 2~10 mass parts of styrene, 2~10 mass parts of divinylbenzene, metering system
Sour 1~4 mass parts of methyl esters, 1~4 mass parts of t-butyl styrene, 0.1~0.6 mass parts of benzoyl peroxide, normal heptane 12~
The mass ratio of 5~12 mass parts of 24 mass parts and dichloroethanes takes each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；
The surfactant can be in odium stearate, neopelex and sodium stearyl sulfate
It is any；
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 40~70 DEG C are heated under stirring, treats that solids is (complete
Portion) after dissolving, then will be uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, peroxide
The mixture for changing benzoyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 80~95 DEG C, (
It is lasting) lower progress suspension polymerization is stirred, (extremely harden, after aging), filter, solids is to surpass after 7~9h of reaction time
The crude product of hydrophobic styrene diethylene benzene copoly mer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 3 is used again
The acetone of~8 times of quality by solids apparatus,Soxhlet's (industrially can use it is existing with identical function effect equipment or
Directly soak) in after 12~48h of extracting, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, form pore structure, then
Solids is sequentially washed with absolute ethyl alcohol, deionized water, is fixed pore structure, obtains porous small ball shape solids；Will
(after purification) porous small ball shape solids is dry, screening, that is, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer is made
Catalyst carrier.
In present disclosure：The dosage quality of organic matter described in step a and inorganic salts mass parts it is preferable to
100:1。
In present disclosure：Styrene, divinylbenzene, methyl methacrylate and the tert-butyl group described in step a
It is preferable to 10 for the dosage quality of styrene mass parts:8.5:3:3.
In present disclosure：The mass parts dosage preferably 0.1 of (initiator) benzoyl peroxide described in step a
~0.15 mass parts.
In present disclosure：Stirred described in step b it is lower carry out suspension polymerization be agitator speed for 60~
Heating is stirred under conditions of 280rpm (rev/min).
In present disclosure：Lower progress suspension polymerization preferably agitator speed is stirred described in step b is
Suspension polymerization is carried out under conditions of 70~125rpm (rev/min).
In present disclosure：Be heated to described in step b temperature be 80~95 DEG C replace be heated to temperature be 87~
92℃。
In present disclosure：It is that solids is suitable that solids described in step c is sequentially washed with deionized water, absolute ethyl alcohol
Secondary to be washed 2~4 times with deionized water, absolute ethyl alcohol respectively, each washing is solids with deionized water, the quality of absolute ethyl alcohol
3~8 times of quality.
In present disclosure：Solids described in step c preferably extracts 24h, extracting acetone with acetone extraction
Quality be 3~8 times of solids quality.
In present disclosure：It is that solids is suitable that solids described in step c is sequentially washed with absolute ethyl alcohol, deionized water
Secondary to be washed 2~4 times with absolute ethyl alcohol, deionized water respectively, each washing is solids with the quality of absolute ethyl alcohol, deionized water
3~8 times of quality.
In present disclosure：It is dry described in step c, sieve be by solids temperature be 50~60 DEG C, pressure be
Dry 12~36h under conditions of 0.08MPa, then sieve and (cross 1mm sieves), i.e., obtained white,Super-hydrophobic highly resistance
Press styrene diethylene benzene copoly mer catalyst carrier.
In present disclosure：The each component raw material used can first carry out refinement treatment：The commercially available of purchase (is purchased from
Aladdin or Mike woods) styrene (abbreviation St) carries out that distillation is refined, and step is as follows before the use：1. by the benzene second of 500mL
Alkene monomer is added in the separatory funnel of 1000mL, is washed three times with the NaOH aqueous solutions of 150mL5%；It is 2. more with deionized water
Secondary washing is put into a little anhydrous MgSO until neutral (pH is 7~8)4It is drying to liquid clarification；3. after above-mentioned drying
Styrene rectification under vacuum, collects the cut after distillation, spare.Divinylbenzene (abbreviation DVB), t-butyl styrene (abbreviation t-
Bu), the distillation process of methyl methacrylate (abbreviation MMA) monomer is as styrene monomer.Benzoyl peroxide is (referred to as
BPO chloroform) is used as solvent, CH3OH makees precipitating reagent, handled using recrystallizing and refining etc..
Compared with prior art, the present invention has following features and beneficial effect：
(1) using the present invention, using styrene, t-butyl styrene as monomer, methyl methacrylate is unmodified function
Monomer, divinylbenzene are crosslinking agent, and benzoyl peroxide is initiator, and normal heptane is pore-foaming agent, and dichloroethanes is solubilizer,
Organic matter (polyvinyl alcohol -1788 etc.) be macromolecule dispersing agent, neopelex etc. for surfactant, help it is scattered
Agent, inorganic salts (calcium phosphate etc.) are inorganic dispersant；The present invention using inorganic salts and water-soluble polymer make composite dispersing agent, with
And anion surfactant makees the synergistic effect between dispersion aids；Utilize introduced function monomer methyl methacrylate
In entrained ester group, its double bond plays strong gain to Pt loads, preferably load played to catalytic active component and is made
With reducing the loss of active component, and the monomer has certain hydrophobicity, it is possible to increase the hydrophobicity of existing SDB；In addition,
Introduced t-butyl styrene, has rigid phenyl ring, and the big steric hindrance tert-butyl group, greatly improves SDB compressive properties and hydrophobicity；
It can be prepared with super-hydrophobicity and high compressive strength, and the porous SDB hydrophobic catalysts of active functional group under the conditions of being somebody's turn to do
Carrier, the reaction system used in this method have the ability of expanding production；
(2) using the present invention, suspension polymerisation is quarternary copolymerized to prepare super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer
Carrier；Suspension polymerisation is substantially by strong stirring and under the action of dispersant, and monomer is dispersed into countless small liquid pearls and is hanged
Float in water, the polymerisation for being triggered by oil-soluble initiator and being carried out.Polymerization system is by hydrophobic monomer, dispersed phase, stabilization
Agent and hydrophobic initiator are formed.In order to make the resin of generation that there is loose structure, it is necessary to add pore-foaming agent into monomer.To work
The load effect of property component is by introducing functional group, double bond is lifted；To be improved hydrophobicity, addition hydrophobicity is strong,
Monomer with rigid nature is lifted；For the solubization of monomer added by reduction, and avoid oil droplet adhesion uneven, pass through addition
The dispersion stabilizer necessarily matched, quantitative inorganic salts realize protection；With styrene, divinylbenzene, methyl methacrylate, uncle
Butylstyrene is quarternary copolymerized monomer, and initiator is dissolved in monomer, then is mixed to form oily mixture (oil phase) with pore-foaming agent,
Oil phase is mixed with having dissolved the aqueous solution (water phase) of dispersion stabilizer inorganic salts etc., is layered；By caused by stirring
Shearing force makes oil phase be dispersed into drop in water phase；Under the conditions of selected temperature, pressure, the reactivity ratio of reaction monomers is respectively less than 1,
Reaction monomers are inclined to copolymerization；And by oil phase existing interfacial tension alternate with water, pearl is formed, is controlled in stir speed (S.S.)
When with the help of Aqueous dispersions stabilizer, obtaining the more uniform particle of size；With the progress of reaction, different strands
Between be constantly cross-linked with each other, gradually form tridimensional network, to a certain extent after, polymer chain cannot dissolve in oil phase
And separate out, it is separated；Polymer is a phase (solid phase) at this time, and remaining monomer and pore-foaming agent are another phase (liquid phase)；Instead
It should continue, solid phase is on the increase, and liquid phase is constantly reduced, and after the completion of reaction, forms globular solids polymer, and pore-foaming agent divides
It is dispersed among sphere；Then the method washed or extracted with solvent removes pore-foaming agent, the space occupied by former pore-foaming agent
For the hole in ball, this some holes interconnects, and absorption resin is provided with larger ratio surface and pore volume；Quarternary copolymerized monomer
The rigid chain segment of introducing, and the double bond containing ester group of bag, make the resin of gained have high resistance to compression ultra-hydrophobicity, so as to be surpassed
The hydrophobic measuring body styrene divinylbenzene copolymerization carrier of height；
(3) suspension polymerization that the present invention uses, has the characteristics that simple and easy to do, disposable proportioning throwing；Using compound point
Powder and the single dispersant of neopelex ratio have more preferable dispersion effect, are easy to stable and uniform oil droplet；Select
The suitable modified monomer of reactivity ratio, it is quarternary copolymerized to realize suspension polymerisation, and synthesis specific surface area is larger, and aperture pore volume suitably carries
Body, under Static water contact angles, and the test of universal testing machine puller system, shows 154.8 ° of super-hydrophobicity, 68.38N's
Compression strength；
(4) it is right using the present invention, obtained super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier
Active component has higher load stability, improves the catalytic performance of catalyst, has and reduces the resistance to mass tranfer of bed, prevents liquid
It is general, and the advantages that improve fluid communication efficiency, the Pt/SDB hydrophobic catalysts that are prepared using product of the present invention as carrier, for weighing
Water proposes the engineering applications such as tritium, waste water detritiation, and high catalytic efficiency, hydrophobic stability are excellent, can room temperature use, using effect is good
It is good；
(5) product preparation process of the present invention is simple, and process is easy, easy to operate, highly practical.
Brief description of the drawings
Fig. 1 is the FTIR spectrum (abbreviation FT-IR) of the quarternary copolymerized modified synthesis carrier of styrene-divinylbenzene
Collection of illustrative plates.As shown in the figure, wherein 3025cm-1Locate as phenyl ring double bond=CH stretching vibrations；2923cm-1Locate as methyl-CH2- asymmetric
Stretching vibration；1731cm-1Locate as the strong stretching vibration of ester group ＞ C=O；1452cm-1Locate to shake for phenyl ring skeleton-C=C- bendings
It is dynamic；1375cm-1Locate as the tert-butyl group-C (CH3) symmetrical deformation vibration；1028cm-1Locate as the in-plane deformation of monosubstituted phenyl ring=CH；
838cm-1Locate as-CH3In-plane deformation；756cm-1Locate as the out-of-plane deformation of monosubstituted phenyl ring=CH；Illustrate styrene, divinyl
The quarternary copolymerized success of benzene, methyl methacrylate, t-butyl styrene；
Fig. 2 is super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer carrier and unmodified styrene-two in blanket of nitrogen
Divinylbenzene copolymer is from room temperature to 800 DEG C thermogravimetric (abbreviation TGA) curve.As seen from the figure, unmodified stryrene divinyl base
Benzene copolymerization carrier starts weightlessness occur after 28.97 DEG C, and super-hydrophobic styrene diethylene benzene copoly mer carrier exists
Just start weightlessness occur after 187.87 DEG C, at 140 DEG C or so, unmodified styrene diethylene benzene copoly mer is weightless
1.02%；Super-hydrophobic styrene diethylene benzene copoly mer is unchanged.When temperature continues to rise, unmodified stryrene divinyl
Base benzene copolymer starts quick weight loss at 369.22 DEG C and decomposes；Super-hydrophobic styrene diethylene benzene copoly mer is in 383.79 DEG C
Start to decompose.This explanation is introducing p-tert-butylstyrene (abbreviation t-Bu), methyl methacrylate (abbreviation MMA) rigid unitary
Afterwards, heat endurance is significantly improved, and super-hydrophobic carrier no matter early period stability at later stage it is excellent.Usual hydrogen aqueous is mutually urged
Change the operation temperature for exchanging (abbreviation LPCE) under 300 DEG C, therefore said catalyst carrier can be used for detritiation system well
In system；
Table 1 is under nitrogen atmosphere, carrier is to N2Adsorption/desorption and obtained parameter under the test of universal testing machine puller system.
Adsorption and desorption isotherms refer under steady temperature that balance adsorption desorption amount and the relation curve by adsorption desorption gas pressure, contain big
Metering-orifice structure and Adsorption thermodynamics information.Known activity component Pt nanoparticle particle diameter is therefore obtained super thin in 1~8nm
Water modified support aperture is more suitable for load active component, beneficial to preparing for catalyst；And compression strength does not change almost
Property 2 times of carrier, the problems such as more preferable effect is played in engineer application, extends catalyst life, reduces broken inactivation；
Table 1：Doping vario-property carrier pore structure parameter
Fig. 3-1 is that super-hydrophobic SDB carriers adsorb nickel ion in the pseudo- first order kinetics figure of Lagrange, Fig. 3-2 is super-hydrophobic
SDB carriers adsorb nickel ion in Lagrangian pseudo-second-order equation figure, are the absorption power using nickel ion simulation active component
Test is learned, super-hydrophobic styrene diethylene benzene copoly mer is contrasted with unmodified styrene diethylene benzene copoly mer carrier.
Table 2 is different carriers to kinetic parameter after nickel ion absorption fitting.Understand, super-hydrophobic carrier and unmodified support are to nickel ion
The compound pseudo- first _ order kinetics equation of Lagrange of adsorption process, whole adsorption reaction belongs to physical absorption, is diffused as limiting it
The principal element of speed, therefore the main resistance for being subject to Liquid film diffusion of absorption of the nickel ion on above-mentioned carrier.With throwing amount
Increase, adsorbance qe reduces, and the trend increased occurs in rate of adsorption k, this is because in adsorption process, throwing amount is more, reaches same
The adsorption reaction fraction F (F=qt/qe) of sample, the required time is fewer, with scheming unanimously.
Table 2：
In table, qe,exp、qe,calThe experiment value and theoretical value of unit mass adsorbance, mg/g when respectively balancing；
k1：Primary adsorption speed constant, min-1；k2：Secondary absorption speed constant, g/ (mgmin)；R2：Fitting coefficient.
Table 3 is to describe two kinds of equilibrium relations between carrier and nickel ion using Langmuir and Freundlich thermoisopleths
And the fitting result such as surface characteristic.According to R2Understand that two carriers can preferably coincide the adsorption process of nickel ion
Langmuir and Freundlich thermoisopleths, are more suitable for being described with Freundlich thermoisopleths, illustrate this two kinds loads
The surface of body is not stable homogeneous, and BET tests also indicate that its specific surface area is big, and aperture is small, illustrates that pore structure is more, and surface is difficult
To reach definitely smooth；Wherein KL is the ratio between absorption and desorption rate, represents the power of adsorption capacity, and the KL values of two kinds of carriers are equal
Just, to illustrate under experiment condition, absorption of the carrier to nickel ion spontaneous can carry out.KF is affinity coefficient, for describe nickel from
The size of bond strength between son and carrier, KF values are bigger, illustrate that carrier is combined more stable with nickel ion, super-hydrophobic carrier pair
The affinity of nickel ion is very strong, this is speculated before meeting, and above-mentioned super-hydrophobic carrier may there are certain between nickel ion
Complexing or bonding relationships, reach stronger adsorption capacity.And the KF values of unmodified support are much smaller than super-hydrophobic carrier, show not
The combination power of modified support and nickel ion is very weak, illustrates that unmodified support only relies on concentration difference and promote to nickel ion absorption and is consistent
Close, between any bonding force is not present.N values are generally related to the property of adsorbent, and 1/n values are smaller, illustrate the easier nickel of carrier
Ion, modifying super hydrophobicity carrier 1/n ＜ 1 in adsorption process, show that the absorption to nickel ion belongs to preferential absorption, unmodified
1/n ＞ 1 of the carrier in adsorption process, illustrates to be difficult to adsorb nickel ion；
Table 3：
In table, ceFor balance mass concentration, mg/L；qeFor equilibrium adsorption capacity, mg；qoCarried for unit quality hydrophobic catalyst
The maximal absorptive capacity of body, mg/g；KL、KFIt is equilibrium adsorption coefficient, represents the relative size of adsorbance；N is characterized constant, table
Show the inhomogeneities on hydrophobic catalyst carrier surface and the relative size of adsorption strength.
Fig. 4 is scanning electron microscope (SEM) photograph (abbreviation SEM) figure of super-hydrophobic carrier, and the lower left corner is respectively carrier table after amplifying 20,000 times
Face situation.First and last, modified support is in 100 times of SEM, and equal visible size is uniform, and sphericity is good, smooth etc. with surface
Property, bead size reach more than 1mm.It can be observed in 20,000 times of figures, super-hydrophobic carrier hole density is small, even in 20,000 times
Lower observation, surface also show smooth, and pore size is homogeneous, and hole is uniform；
Fig. 5-1 is SDB Static water contact angles, 5-2 is that super-hydrophobic SDB Static water contact angles are Static water contact angles test
Figure, it can be seen that super-hydrophobic carrier contact angle reaches 154.8 °, and unmodified support Static water contact angles are only 130.10 °, significantly
Improve.
Embodiment
The invention will be further described for example given below plan, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes the present invention according to the content of the invention described above
It is whole, still fall within protection scope of the present invention.
Embodiment 1：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
400g deionized waters, 4g polyvinyl alcohol -1788,0.01g calcium phosphate, the 12 of 0.12g are added in three-necked flask
Sodium alkyl benzene sulfonate, is made into uniform water phase, and stirring, is heated to 60 DEG C, after all dissolving, then will be uniformly mixed
10gSt (i.e. styrene), 8.5gDVB (i.e. divinylbenzene), 3gMMA (i.e. methyl methacrylate), 3gt-Bu (the i.e. tert-butyl groups
Styrene), 0.15gBPO (i.e. benzoyl peroxide), 24g normal heptanes and 11.6g dichloroethanes be added in there-necked flask, adjust
Required rotating speed is 70rpm/min, is to slowly warm up to 87 DEG C, progress suspension polymerization under stirring, after reaction time 7h, filtering,
Solids is the crude product of styrene diethylene benzene copoly mer；Solids is sequentially washed with deionized water, absolute ethyl alcohol
Wash, then after solids to extract in apparatus,Soxhlet's to the acetone of 3 times of quality of solids quality 12h, filtering, then by solid
Thing is sequentially washed with absolute ethyl alcohol, deionized water, then by solids is dry, screening, that is, super-hydrophobic high resistance to compression styrene-two is made
Divinylbenzene copolymer hydrophobic catalyst carrier.
Embodiment 2：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
400g deionized waters, 6g polyvinyl alcohol -1788,0.01g calcium phosphate, the dodecane of 0.1g are added in three-necked flask
Base benzene sulfonic acid sodium salt, is made into uniform water phase, and stirring, is heated to 60 DEG C, after all dissolving, then by uniformly mixed 10gSt,
8.5gDVB, 3gMMA, 3gt-Bu, 0.15gBPO, 24g normal heptane and 11.6g dichloroethanes are added in there-necked flask, needed for adjustment
Rotating speed is 70rpm/min, is heated to 87 DEG C, progress suspension polymerization under stirring, and after reaction time 8h, is filtered, solids is
For the crude product of styrene diethylene benzene copoly mer；Solids is sequentially washed with deionized water, absolute ethyl alcohol, then with admittedly
The acetone of 5 times of quality of body amount of substance solids extracts in apparatus,Soxhlet's to 24h after, filtering, then solids is sequentially used
Absolute ethyl alcohol, deionized water washing, then by solids is dry, screening, that is, super-hydrophobic high resistance to compression styrene-divinylbenzene is made
Copolymer hydrophobic catalyst carrier.
Embodiment 3：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
400g deionized waters, 6g polyvinyl alcohol -1788,0.01g calcium phosphate, the dodecane of 0.1g are added in three-necked flask
Base benzene sulfonic acid sodium salt, is made into uniform water phase, and stirring, is heated to 60 DEG C, after all dissolving, then by uniformly mixed 10gSt,
8.5gDVB, 3gMMA, 3gt-Bu, 0.15gBPO, 24g normal heptane and 11.6g dichloroethanes are added in there-necked flask, needed for adjustment
Rotating speed is 70rpm/min, is heated to 87 DEG C, progress suspension polymerization under stirring, and after reaction time 9h, is filtered, solids is
For the crude product of styrene diethylene benzene copoly mer；Solids is sequentially washed with deionized water, absolute ethyl alcohol, then with admittedly
The acetone of 8 times of quality of body amount of substance solids extracts in apparatus,Soxhlet's to 48h after, filtering, then solids is sequentially used
Absolute ethyl alcohol, deionized water washing, then by solids is dry, screening, that is, super-hydrophobic high resistance to compression styrene-divinylbenzene is made
Copolymer hydrophobic catalyst carrier.
Embodiment 4：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
400g deionized waters, 6g polyvinyl alcohol -2499,0.01g calcium phosphate, the dodecane of 0.1g are added in three-necked flask
Base benzene sulfonic acid sodium salt, is made into uniform water phase, and stirring, is heated to 60 DEG C, after all dissolving, then by uniformly mixed 10gSt,
8.5gDVB, 3gMMA, 3gt-Bu, 0.15gBPO, 24g normal heptane and 11.6g dichloroethanes are added in there-necked flask, needed for adjustment
Rotating speed is 70rpm/min, is heated to 87 DEG C, progress suspension polymerization under stirring, and after reaction time 7h, is filtered, solids is
For the crude product of styrene diethylene benzene copoly mer；Solids is sequentially washed with deionized water, absolute ethyl alcohol, then with admittedly
The acetone of 5 times of quality of body amount of substance solids extracts in apparatus,Soxhlet's to 48h after, filtering, then solids is sequentially used
Absolute ethyl alcohol, deionized water washing, then by solids is dry, screening, that is, super-hydrophobic high resistance to compression styrene-divinylbenzene is made
Copolymer catalyst carrier.
Embodiment 5~7：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, organic matter point
It is not hydroxyethyl cellulose, gelatin, sodium carboxymethylcellulose, the corresponding dosage of each species is 4g, 2g, 1g；Inorganic salts
It is magnesium carbonate, anhydrous sodium sulfate, calcium hydroxy phosphate respectively, dosage is 0.05g；Surfactant is odium stearate, ten respectively
Dialkyl benzene sulfonic acids sodium, octadecyl, dosage are 0.1g；Other component raw materials and dosage, reaction condition etc. with embodiment 1
It is identical, omit.
Embodiment 8~13：
Mixing speed is respectively 60rpm, 85rpm, 100rpm, 125rpm, 165rpm, 280rpm；It is other with embodiment 1
It is identical, omit.
Embodiment 14~17：
Initiator B PO (i.e. benzoyl peroxide) dosage is respectively 0.1g, 0.15g, 0.2g, 0.6g；Other component raw materials
And dosage, reaction condition are same as Example 1, omit.
Embodiment 18~20：
It is respectively 70~75 DEG C, 75~80 DEG C, 85~90 DEG C to be heated to suspension polymerization temperature；It is other and embodiment
1 is identical, omits.
Embodiment 21~24：
Methyl methacrylate, t-butyl styrene dosage are respectively 4g, 3g, 2g, 1g；Other component raw materials and dosage,
Reaction condition is same as Example 1, omits.
Embodiment 25：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 200 mass parts of deionized water, 2 mass parts of organic matter, 0.03 mass parts of inorganic salts, surfactant
0.1 mass parts, 8 mass parts of styrene, 8 mass parts of divinylbenzene, 2 mass parts of t-butyl styrene, methyl methacrylate 2
Mass parts, the mass ratio of 10 mass parts of 0.1 mass parts of benzoyl peroxide, 15 mass parts of normal heptane and dichloroethanes take respectively
Component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 40~70 DEG C are heated under stirring, treats that solids is (complete
Portion) after dissolving, then will be uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, peroxide
The mixture for changing benzoyl, normal heptane and dichloroethanes is added in reaction vessel, temperature is heated to as 90 DEG C, under stirring
Suspension polymerization is carried out, (is extremely hardened, after aging) after reaction time 8h, filtering, solids is super-hydrophobic styrene-diethyl
The crude product of alkenyl benzene copolymer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 6 is used again
Solids (can industrially be used the existing equipment with identical function effect or directly by the acetone of times quality in apparatus,Soxhlet's
Immersion) in after extracting 30h, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, pore structure is formed, then by solids
Sequentially washed with absolute ethyl alcohol, deionized water, be fixed pore structure, obtain porous small ball shape solids；Will be (after purification
) porous small ball shape solids is dry, sieves, that is, (white) super-hydrophobic high resistance to compression styrene-divinylbenzene copolymerization is made
Thing catalyst carrier.
Embodiment 26：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 200 mass parts of deionized water, 3 mass parts of organic matter, 0.01 mass parts of inorganic salts, surfactant
0.1 mass parts, 8 mass parts of styrene, 6 mass parts of divinylbenzene, 3 mass parts of methyl methacrylate, t-butyl styrene 3
Mass parts, the mass ratio of 5 mass parts of 0.15 mass parts of benzoyl peroxide, 10 mass parts of normal heptane and dichloroethanes take respectively
Component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 60 DEG C are heated under stirring, treats that solids (whole) is molten
Xie Hou, then by uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, benzoyl peroxide first
The mixture of acyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 80 DEG C, is hanged under stirring
Polymerisation is floated, (is extremely hardened, after aging) after reaction time 9h, filtering, solids is super-hydrophobic styrene-divinylbenzene
The crude product of copolymer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 3 is used again
Solids (can industrially be used the existing equipment with identical function effect or directly by the acetone of times quality in apparatus,Soxhlet's
Immersion) in after extracting 48h, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, pore structure is formed, then by solids
Sequentially washed with absolute ethyl alcohol, deionized water, be fixed pore structure, obtain porous small ball shape solids；Will be (after purification
) porous small ball shape solids is dry, sieves, that is, (white) super-hydrophobic high resistance to compression styrene-divinylbenzene copolymerization is made
Thing catalyst carrier.
Embodiment 27：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 200 mass parts of deionized water, 4 mass parts of organic matter, 0.05 mass parts of inorganic salts, surfactant
0.1 mass parts, 10 mass parts of styrene, 10 mass parts of divinylbenzene, 1 mass parts of methyl methacrylate, tert-butyl benzene second
1 mass parts of alkene, the mass ratio of 12 mass parts of 0.6 mass parts of benzoyl peroxide, 13 mass parts of normal heptane and dichloroethanes take
Each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 50 DEG C are heated under stirring, treats that solids (whole) is molten
Xie Hou, then by uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, benzoyl peroxide first
The mixture of acyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 85 DEG C, is hanged under stirring
Polymerisation is floated, (is extremely hardened, after aging) after reaction time 8h, filtering, solids is super-hydrophobic styrene-divinylbenzene
The crude product of copolymer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 8 is used again
Solids (can industrially be used the existing equipment with identical function effect or directly by the acetone of times quality in apparatus,Soxhlet's
Immersion) in after extracting 12h, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, pore structure is formed, then by solids
Sequentially washed with absolute ethyl alcohol, deionized water, be fixed pore structure, obtain porous small ball shape solids；Will be (after purification
) porous small ball shape solids is dry, sieves, that is, (white) super-hydrophobic high resistance to compression styrene-divinylbenzene copolymerization is made
Thing catalyst carrier.
Embodiment 28~34：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 200~400 mass parts of deionized water, 1~5 mass parts of organic matter, 0.01~0.05 mass of inorganic salts
Part, 0.1~0.6 mass parts of surfactant, 2~10 mass parts of styrene, 2~10 mass parts of divinylbenzene, metering system
Sour 1~4 mass parts of methyl esters, 1~4 mass parts of t-butyl styrene, 0.1~0.6 mass parts of benzoyl peroxide, normal heptane 12~
The mass ratio of 5~12 mass parts of 24 mass parts and dichloroethanes takes each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
The specific mass parts dosage of each component raw material see the table below in each embodiment：
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 40~70 DEG C are heated under stirring, treats that solids is (complete
Portion) after dissolving, then will be uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, peroxide
The mixture for changing benzoyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 80~95 DEG C, (
It is lasting) lower progress suspension polymerization is stirred, (extremely harden, after aging), filter, solids is to surpass after 7~9h of reaction time
The crude product of hydrophobic styrene diethylene benzene copoly mer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 3 is used again
The acetone of~8 times of quality by solids apparatus,Soxhlet's (industrially can use it is existing with identical function effect equipment or
Directly soak) in after 12~48h of extracting, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, form pore structure, then
Solids is sequentially washed with absolute ethyl alcohol, deionized water, is fixed pore structure, obtains porous small ball shape solids；Will
(after purification) porous small ball shape solids is dry, screening, that is, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer is made
Catalyst carrier.
Embodiment 35：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 200 mass parts of deionized water, 1 mass parts of organic matter, 0.01 mass parts of inorganic salts, surfactant
0.1 mass parts, 2 mass parts of styrene, 2 mass parts of divinylbenzene, 1 mass parts of methyl methacrylate, t-butyl styrene 1
Mass parts, the mass ratio of 5 mass parts of 0.1 mass parts of benzoyl peroxide, 12 mass parts of normal heptane and dichloroethanes take each group
Divide raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 40 DEG C are heated under stirring, treats that solids (whole) is molten
Xie Hou, then by uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, benzoyl peroxide first
The mixture of acyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 80 DEG C, (continuing) stirring
Lower carry out suspension polymerization, after reaction time 9h (to hardening, aging), filtering, solids is super-hydrophobic styrene-two
The crude product of divinylbenzene copolymer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 3 is used again
Solids (can industrially be used the existing equipment with identical function effect or directly by the acetone of times quality in apparatus,Soxhlet's
Immersion) in after extracting 48h, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, pore structure is formed, then by solids
Sequentially washed with absolute ethyl alcohol, deionized water, be fixed pore structure, obtain porous small ball shape solids；Will be (after purification
) porous small ball shape solids is dry, sieves, that is, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst is made
Carrier.
Embodiment 36：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 400 mass parts of deionized water, 6 mass parts of organic matter, 0.05 mass parts of inorganic salts, surfactant
0.6 mass parts, 10 mass parts of styrene, 10 mass parts of divinylbenzene, 4 mass parts of methyl methacrylate, tert-butyl benzene second
4 mass parts of alkene, the mass ratio of 12 mass parts of 0.6 mass parts of benzoyl peroxide, 24 mass parts of normal heptane and dichloroethanes take
Each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 70 DEG C are heated under stirring, treats that solids (whole) is molten
Xie Hou, then by uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, benzoyl peroxide first
The mixture of acyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 95 DEG C, (continuing) stirring
Lower carry out suspension polymerization, after reaction time 7h (to hardening, aging), filtering, solids is super-hydrophobic styrene-two
The crude product of divinylbenzene copolymer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 8 is used again
Solids (can industrially be used the existing equipment with identical function effect or directly by the acetone of times quality in apparatus,Soxhlet's
Immersion) in after extracting 12h, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, pore structure is formed, then by solids
Sequentially washed with absolute ethyl alcohol, deionized water, be fixed pore structure, obtain porous small ball shape solids；Will be (after purification
) porous small ball shape solids is dry, sieves, that is, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst is made
Carrier.
Embodiment 37：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 300 mass parts of deionized water, 3.5 mass parts of organic matter, 0.03 mass parts of inorganic salts, surface-active
0.35 mass parts of agent, 6 mass parts of styrene, 6 mass parts of divinylbenzene, 2.5 mass parts of methyl methacrylate, tert-butyl benzene
The quality of 2.5 mass parts of ethene, 9 mass parts of 0.35 mass parts of benzoyl peroxide, 18 mass parts of normal heptane and dichloroethanes
Than taking each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 55 DEG C are heated under stirring, treats that solids (whole) is molten
Xie Hou, then by uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, benzoyl peroxide first
The mixture of acyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 88 DEG C, (continuing) stirring
Lower carry out suspension polymerization, after reaction time 8h (to hardening, aging), filtering, solids is super-hydrophobic styrene-two
The crude product of divinylbenzene copolymer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 6 is used again
Solids (can industrially be used the existing equipment with identical function effect or directly by the acetone of times quality in apparatus,Soxhlet's
Immersion) in after extracting 30h, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, pore structure is formed, then by solids
Sequentially washed with absolute ethyl alcohol, deionized water, be fixed pore structure, obtain porous small ball shape solids；Will be (after purification
) porous small ball shape solids is dry, sieves, that is, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst is made
Carrier.
Embodiment 38~44：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 200~400 mass parts of deionized water, 1~6 mass parts of organic matter, 0.01~0.05 mass of inorganic salts
Part, 0.1~0.6 mass parts of surfactant, 2~10 mass parts of styrene, 2~10 mass parts of divinylbenzene, metering system
Sour 1~4 mass parts of methyl esters, 1~4 mass parts of t-butyl styrene, 0.1~0.15 mass parts of benzoyl peroxide, normal heptane 12
The mass ratio of 5~12 mass parts of~24 mass parts and dichloroethanes takes each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
The specific mass parts dosage of each component raw material see the table below in each embodiment：
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 40~70 DEG C are heated under stirring, treats that solids is (complete
Portion) after dissolving, then will be uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, peroxide
The mixture for changing benzoyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 80~95 DEG C, (
It is lasting) lower progress suspension polymerization is stirred, (extremely harden, after aging), filter, solids is to surpass after 7~9h of reaction time
The crude product of hydrophobic styrene diethylene benzene copoly mer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 3 is used again
The acetone of~8 times of quality by solids apparatus,Soxhlet's (industrially can use it is existing with identical function effect equipment or
Directly soak) in after 12~48h of extracting, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, form pore structure, then
Solids is sequentially washed with absolute ethyl alcohol, deionized water, is fixed pore structure, obtains porous small ball shape solids；Will
(after purification) porous small ball shape solids is dry, screening, that is, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer is made
Catalyst carrier.
Embodiment 45：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 300 mass parts of deionized water, 5 mass parts of organic matter, 0.05 mass parts of inorganic salts, surfactant
0.4 mass parts, 10 mass parts of styrene, 8.5 mass parts of divinylbenzene, 3 mass parts of methyl methacrylate, tert-butyl benzene second
3 mass parts of alkene, the mass ratio of 9 mass parts of 0.3 mass parts of benzoyl peroxide, 20 mass parts of normal heptane and dichloroethanes take
Each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 60 DEG C are heated under stirring, treats that solids (whole) is molten
Xie Hou, then by uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, benzoyl peroxide first
The mixture of acyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 88 DEG C, (continuing) stirring
Lower carry out suspension polymerization, after reaction time 8h (to hardening, aging), filtering, solids is super-hydrophobic styrene-two
The crude product of divinylbenzene copolymer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 6 is used again
Solids (can industrially be used the existing equipment with identical function effect or directly by the acetone of times quality in apparatus,Soxhlet's
Immersion) in after extracting 33h, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, pore structure is formed, then by solids
Sequentially washed with absolute ethyl alcohol, deionized water, be fixed pore structure, obtain porous small ball shape solids；Will be (after purification
) porous small ball shape solids is dry, sieves, that is, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst is made
Carrier.
Embodiment 46：
A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, step are：
A, dispensing：By 300 mass parts of deionized water, 4 mass parts of organic matter, 0.04 mass parts of inorganic salts, surfactant
0.3 mass parts, 10 mass parts of styrene, 8.5 mass parts of divinylbenzene, 3 mass parts of methyl methacrylate, tert-butyl benzene second
The mass ratio of 3 mass parts of alkene, 10 mass parts of 0.15 mass parts of benzoyl peroxide, 20 mass parts of normal heptane and dichloroethanes
Take each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be appointing in calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate
It is a kind of；The surfactant can be any in odium stearate, neopelex and sodium stearyl sulfate
Kind；
B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts
With surfactant be added to reaction vessel (such as：Three-necked flask) in, 55 DEG C are heated under stirring, treats that solids (whole) is molten
Xie Hou, then by uniformly mixed styrene, divinylbenzene, methyl methacrylate, t-butyl styrene, benzoyl peroxide first
The mixture of acyl, normal heptane and dichloroethanes is added in reaction vessel, is heated to temperature as 90 DEG C, (continuing) stirring
Lower carry out suspension polymerization, after reaction time 8h (to hardening, aging), filtering, solids is super-hydrophobic styrene-two
The crude product of divinylbenzene copolymer；
C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：Consolidate what is obtained after reaction
Body thing (crude product of i.e. super-hydrophobic styrene diethylene benzene copoly mer) is sequentially washed with deionized water, absolute ethyl alcohol, with except
Remove the impurity such as responseless styrene and divinylbenzene monomers and organic matter solubility dispersant；Solids quality 6 is used again
Solids (can industrially be used the existing equipment with identical function effect or directly by the acetone of times quality in apparatus,Soxhlet's
Immersion) in after extracting 38h, filtering, to remove the organic impurities such as pore-foaming agent and solubilizer, pore structure is formed, then by solids
Sequentially washed with absolute ethyl alcohol, deionized water, be fixed pore structure, obtain porous small ball shape solids；Will be (after purification
) porous small ball shape solids is dry, sieves, that is, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst is made
Carrier.
In above-described embodiment 25~44：Styrene, divinylbenzene, methyl methacrylate, Yi Jishu described in step a
It is preferable to 10 for the dosage quality of butylstyrene mass parts:8.5:3:3.
In above-described embodiment 25~46：It is that agitator speed can be with that the lower suspension polymerization that carries out is stirred described in step b
To be stirred heating under conditions of 60~280rpm (rev/min), preferably for 70~125rpm (rev/min) under conditions of
Carry out suspension polymerization.
In above-described embodiment 28~34,38~44：Temperature is heated to described in step b to replace with and be heated to for 80~95 DEG C
Temperature is 87~92 DEG C.
In above-described embodiment：Solids described in step c sequentially washed with deionized water, absolute ethyl alcohol be solids sequentially
Washed 2~4 times with deionized water, absolute ethyl alcohol respectively, each washing is solid matter with deionized water, the quality of absolute ethyl alcohol
3~8 times of amount.
In above-described embodiment 25~44：Solids described in step c preferably extracts 24h with acetone extraction, and extracting is used
The quality of acetone can be 3~8 times of solid matter amount.
In above-described embodiment：Solids described in step c sequentially washed with absolute ethyl alcohol, deionized water be solids sequentially
Washed 2~4 times with absolute ethyl alcohol, deionized water respectively, each washing is solid matter with the quality of absolute ethyl alcohol, deionized water
3~8 times of amount.
In above-described embodiment：It is dry described in step c, sieve be by solids temperature be 50~60 DEG C, pressure be
Dry 12~36h under conditions of 0.08MPa, then sieve and (cross 1mm sieves), i.e., obtained white,Super-hydrophobic highly resistance
Press styrene diethylene benzene copoly mer catalyst carrier.
In above-described embodiment：The each component raw material used can first carry out refinement treatment：Purchase it is commercially available (be purchased from Ah
Latin or Mike woods) styrene (abbreviation St) carries out that distillation is refined, and step is as follows before the use：1. by the styrene of 500mL
Monomer is added in the separatory funnel of 1000mL, is washed three times with the NaOH aqueous solutions of 150mL5%；It is 2. multiple with deionized water
Washing is put into a little anhydrous MgSO until neutral (pH is 7~8)4It is drying to liquid clarification；3. the benzene after above-mentioned drying
Ethene rectification under vacuum, collects the cut after distillation, spare.Divinylbenzene (abbreviation DVB), t-butyl styrene (abbreviation t-
Bu), the distillation process of methyl methacrylate (abbreviation MMA) monomer is as styrene monomer.Benzoyl peroxide is (referred to as
BPO chloroform) is used as solvent, CH3OH makees precipitating reagent, handled using recrystallizing and refining etc..
In above-described embodiment：Used each raw material is commercial product.
In above-described embodiment：It is especially not dated in used percentage, be quality (weight) percentage or
Well known to a person skilled in the art percentage；Described quality (weight) part can be gram.
In above-described embodiment：Technological parameter (temperature, time, rotating speed etc.) and each component numerical quantity in each step etc. are
Scope, any point is applicable.
The technology contents being not specifically delineated in present invention and above-described embodiment are compared with technology.
It can implement the invention is not restricted to above-described embodiment, described in present invention and there is the good result.
Claims (10)
- A kind of 1. preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier, it is characterized in that step Suddenly it is：A, dispensing：By 200~400 mass parts of deionized water, 1~6 mass parts of organic matter, 0.01~0.05 mass parts of inorganic salts, 0.1~0.6 mass parts of surfactant, 2~10 mass parts of styrene, 2~10 mass parts of divinylbenzene, methacrylic acid 1~4 mass parts of methyl esters, 1~4 mass parts of t-butyl styrene, 0.1~0.6 mass parts of benzoyl peroxide, normal heptane 12~24 The mass ratio of 5~12 mass parts of mass parts and dichloroethanes takes each component raw material；The organic matter is polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -2699, hydroxyl second Any of base cellulose, gelatin and sodium carboxymethylcellulose；The inorganic salts are any of calcium phosphate, magnesium carbonate, sodium chloride, anhydrous sodium sulfate and calcium hydroxy phosphate；The surfactant is any of odium stearate, neopelex and sodium stearyl sulfate；B, the crude product of super-hydrophobic styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts and table Face activating agent is added in reaction vessel, and 40~70 DEG C are heated under stirring, after solids dissolving, then the benzene second that will have been mixed Alkene, divinylbenzene, methyl methacrylate, t-butyl styrene, benzoyl peroxide, normal heptane and dichloroethanes Mixture is added in reaction vessel, is heated to temperature as 80~95 DEG C, stirs lower progress suspension polymerization, reaction time 7 After~9h, filtering, solids is the crude product of super-hydrophobic styrene diethylene benzene copoly mer；C, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier is prepared：The solids that will be obtained after reaction Sequentially washed with deionized water, absolute ethyl alcohol；Again with the acetone of 3~8 times of quality of solids quality by solids in surname extraction In device extract 12~48h after, filtering, then solids is sequentially washed with absolute ethyl alcohol, deionized water, obtains porous small ball shape Solids；By the drying of porous small ball shape solids, screening, that is, super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer is made Catalyst carrier.
- 2. the preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier as described in claim 1, It is characterized in that：Organic matter described in step a and the dosage mass ratio of inorganic salts mass parts are 100:1.
- 3. the preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier as described in claim 1, It is characterized in that：Styrene described in step a, divinylbenzene, methyl methacrylate and t-butyl styrene mass parts Dosage mass ratio is 10:8.5:3:3.
- 4. the preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier as described in claim 1, It is characterized in that：The mass parts dosage of benzoyl peroxide described in step a is 0.1~0.15 mass parts.
- 5. the preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier as described in claim 1, It is characterized in that：It is under conditions of agitator speed is 60~280rpm that the lower suspension polymerization that carries out is stirred described in step b It is stirred heating.
- 6. the preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier as described in claim 1, It is characterized in that：It is under conditions of agitator speed is 70~125rpm that the lower suspension polymerization that carries out is stirred described in step b Carry out suspension polymerization.
- 7. the preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier as described in claim 1, It is characterized in that：It is heated to temperature described in step b and is 80~95 DEG C replacing with that to be heated to temperature be 87~92 DEG C.
- 8. the preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier as described in claim 1, It is characterized in that：It is that solids sequentially uses deionization respectively that solids described in step c is sequentially washed with deionized water, absolute ethyl alcohol Water, absolute ethyl alcohol wash 2~4 times, and each washing is with deionized water, 3~8 times that the quality of absolute ethyl alcohol is solids quality.
- 9. the preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier as described in claim 1, It is characterized in that：It is solids sequentially respectively with anhydrous second that solids described in step c is sequentially washed with absolute ethyl alcohol, deionized water Alcohol, deionized water are washed 2~4 times, and each washing is with 3~8 times that the quality of absolute ethyl alcohol, deionized water is solids quality.
- 10. the preparation side of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier as described in claim 1 Method, it is characterized in that：Dry described in step c, screening is in the bar that temperature is 50~60 DEG C, pressure is 0.08MPa by solids Dry 12~36h under part, then sieve.
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| CN113234187A (en) * | 2021-05-17 | 2021-08-10 | 西南科技大学 | Preparation method of nano-silica hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier material |
| CN115672409A (en) * | 2022-11-10 | 2023-02-03 | 广州启轩新材料科技有限公司 | Method for preparing Pt/SDB hydrophobic catalyst by hydrazine hydrate reduction |
| CN115888820A (en) * | 2022-11-10 | 2023-04-04 | 广州启轩新材料科技有限公司 | Method for preparing Pt/SDB hydrophobic catalyst by sodium borohydride reduction |
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