CN107321384A - The preparation method and applications of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst - Google Patents
The preparation method and applications of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst Download PDFInfo
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- CN107321384A CN107321384A CN201710498150.3A CN201710498150A CN107321384A CN 107321384 A CN107321384 A CN 107321384A CN 201710498150 A CN201710498150 A CN 201710498150A CN 107321384 A CN107321384 A CN 107321384A
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- acid
- sodium alginate
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- solid waste
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- 150000002148 esters Chemical class 0.000 title claims abstract description 85
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 57
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 57
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002910 solid waste Substances 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004137 mechanical activation Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 230000032050 esterification Effects 0.000 claims abstract description 22
- 238000005886 esterification reaction Methods 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 18
- 239000007790 solid phase Substances 0.000 claims abstract description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000011282 treatment Methods 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000000227 grinding Methods 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000002351 wastewater Substances 0.000 claims description 14
- 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 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 229960001126 alginic acid Drugs 0.000 claims description 12
- 239000000783 alginic acid Substances 0.000 claims description 12
- 235000010443 alginic acid Nutrition 0.000 claims description 12
- 229920000615 alginic acid Polymers 0.000 claims description 12
- 150000004781 alginic acids Chemical class 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 11
- 240000003183 Manihot esculenta Species 0.000 claims description 9
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 9
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 8
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 8
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011425 bamboo Substances 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- 241000609240 Ambelania acida Species 0.000 claims description 5
- 150000001413 amino acids Chemical class 0.000 claims description 5
- 239000010905 bagasse Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 229920002522 Wood fibre Polymers 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 8
- 238000004065 wastewater treatment Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 238000000465 moulding Methods 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 12
- 238000003746 solid phase reaction Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 241001330002 Bambuseae Species 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- -1 which is added Chemical compound 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920001282 polysaccharide Polymers 0.000 description 5
- 239000005017 polysaccharide Substances 0.000 description 5
- 150000004804 polysaccharides Chemical class 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229960005137 succinic acid Drugs 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910017343 Fe2 (SO4)3 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005284 basis set Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 210000003128 head Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- B01J35/612—Surface area less than 10 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
- B01J35/638—Pore volume more than 1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides the preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, applied to field of waste water treatment.Cellulosic solid waste is first dried, crushed by this method, obtain cellulosic solid waste powder, it is well mixed again with esterifying agent, molysite and/or ferrous salt, add in mechanical activation solid phase reactor, ball milling simultaneously carries out esterification, separation esterification products and abrading-ball, obtains after lignocellulosic ester admixture, it is added under conditions of stirring in sodium alginate soln, obtains blended liquid；Blended liquid is instilled in calcium chloride solution, crosslinking curing, filtering, and gel ball solidified, load iron is dried, produces target product.The present invention, for raw material, is turned waste into wealth with cellulosic solid waste etc., the treatment of wastes with processes of wastes against one another, recycling, the higher value application of cellulosic solid waste are realized, products therefrom can produce Fenton effect, and be loose structure, water treatment effect is excellent, non-secondary pollution, repeats utilization rate high.
Description
Technical field
The invention belongs to field of waste water treatment, it is related to lignocellulosic modification, specifically lignocellulosic ester/sea
The preparation method and applications of mosanom complex spherical class fenton catalyst.
Background technology
With chemical industry and its high speed development of related industry, especially chemical industry, agricultural chemicals, medicine, papermaking, printing and dyeing, smelting
The development of the industries such as gold, a large amount of industrial wastewaters not standard discharge causes the section in the whole nation more than 1/3rd to be contaminated, and 90%
Urban waters above are seriously polluted, and nearly 50% key cities water head site does not meet drinking water standard.Wherein, organic wastewater
Type and quantity are increasing, and existence time length, migration circle are wide in water, handle for the organic pollution of these difficult for biological degradation
Difficulty is big, and the harm to ecological environment and human health is increasingly serious, and traditional treatment technology is difficult to meet higher and higher ring
Guaranteed request.Therefore, the technology developed efficiently, economic has been compeled for handling difficult for biological degradation, highly toxic organic pollutant wastewater
In the eyebrows and eyelashes.High-level oxidation technology is a kind of New Wastewater Treatment Technology art, active extremely strong using what is produced in chemical reaction process
Free radical (such as OH, HO2Deng) organic pollution macromolecular is degraded to low toxicity or nontoxic small molecule, or even directly
Mineralising is connect for water and carbon dioxide.The effect of deep oxidation degraded is reached, it is necessary to efficient oxidation catalyst.Conventional at present
Containing heavy metal catalyst, easily in the solution, catalyst is difficult to biodegradation to residual after, causes secondary pollution more, and
And high is required to pH value, therefore complex operation, processing cost are higher.
Processing difficult degradation industrial organic waste water mainly uses Fenton (Fenton) oxidation technology, but Fenton oxygen at present
There are still following not enough in use for change system：
1st, Fenton processing labor intensity is big：Hydrogen peroxide operation difficulty is big, and it must be solid that ferrous sulfate, which is added, and sulfuric acid is sub-
Iron iron content 20% or so, relative to 11% iron content of Polyferric Sulfate, considerably increases Treatment of Sludge intensity；
2nd, the cost of Fenton processing is high, and sludge is more：The oxidation of hydrogen peroxide, which can not give full play to, makes reagent cost higher,
And ferrous sulfate adds the amount sludge brought, processing cost it is high (cost that present most enterprises are calculated toward contact not
Including sludge increase), in addition with equipment depreciation, maintenance cost etc.；
3rd, Fenton processing easily returns color：Dosage such as hydrogen peroxide and ferrous sulfate is bad with adding ratio control, or three
Valency iron does not precipitate the aqueous solution being easily caused after processing and shows slightly yellow or yellowish-brown；
4th, Fenton processing corrosivity is big：Hydrogen peroxide has strong oxidizing property, and its oxidisability is only second to fluorine gas, can aoxidize equipment
Corrosion, if protection is bad a certain degree of corrosion to human body；
5th, it can not reuse.
Publication No. CN104646062A Chinese invention patent application, the applying date 2015 year 02 month 12, publication date
On 05 27th, 2015, a kind of plain basis set of bamboo pulp fiber was described into fenton catalyst Fe3+C2O4/ R preparation method, main points
It is to be coordinated to form complex compound Fe by ferric iron and oxalic acid3+C2O4/ R, then it is carried on the bamboo pulp fiber synthesized by bamboo pulpboard
On plain base porous resin R, integrated fenton catalyst Fe is formed3+C2O4/ R, can accelerate catalyzing hydrogen peroxide to drop under visible light
Solve dye class organic pollution in dyeing waste water.The patent application do not disclosed in embodiment its how to carry out wastewater treatment and
The data result of processing, it is impossible to learn its effect.
Publication No. CN105289527A Chinese invention patent applications, December 03 2015 applying date, publication date 2016
In 03 day 02 month year, a kind of preparation method of cellulose esters aerogel material is described, using cellulose as raw material, with long chain fatty acids
Acyl chlorides is esterifying reagent, and carrying out esterification modification to cellulose prepares cellulose esters, and cellulose esters is dissolved in certain solvent, then is passed through
Solvent reclamation exchanges and prepares cellulose esters aeroge sorbing material.This method is non-solid phase reaction, using compared with multi-solvent.
China has abundant lignocellulosic sources, and southern each province is especially prominent, source such as sugarcane, cassava, wood chip, bamboo
Bits, stalk, ramulus mori etc..Resource is made full use of, the renewable new material of high added value is prepared, meets national development recycling economy political affairs
Plan, has important practical significance
The content of the invention
An object of the present invention be just to provide a kind of catalysis efficiency it is high, without heavy metal ion, simple production process and
Can by lignocellulosic comprehensively utilize get up lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, and by its
For handling waste water.
The concrete scheme of the present invention is as follows：
Cellulosic solid waste is dried, crushed, and obtains cellulosic solid waste powder；
Cellulosic solid waste powder, esterifying agent, molysite and/or ferrous salt, are well mixed, obtain mixture；
Mixture is added in mechanical activation solid phase reactor, and ball milling simultaneously carries out esterification, separation esterification products and abrading-ball,
Obtain lignocellulosic ester admixture；
Lignocellulosic ester admixture is added in sodium alginate soln under conditions of stirring, obtains blended liquid；
Blended liquid is instilled in calcium chloride solution, crosslinking curing, filtering, and gel ball solidified, load iron is dried,
Produce target product lignocellulosic ester/sodium alginate complex spherical class fenton catalyst.
Further, cellulosic solid waste powder：Esterifying agent：Molysite and/or ferrous salt=100：5-30：1-8, the ratio
It is mass ratio.
Further, the mass ratio of lignocellulosic ester admixture and sodium alginate is 4-8：1, the matter of sodium alginate soln
Amount concentration is 1-5%.
Further, esterifying agent includes oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, horse
Come any of sour, butene dioic acid, glutaconate, malic acid, amino acid, citric acid or two or more combinations.Esterifying agent
Occurs esterification with cellulosic solid waste.
Further, the molysite is FeCl3、Fe(NO3)3、Fe2(SO4)3Any of or two or more combinations,
The ferrous salt is FeCl2、Fe(NO3)2、FeSO4Any of or two or more combinations, the effect of molysite or ferrous salt
There are two aspects, one is the esterification for being catalyzed lignocellulosic, and two are carried on target product, play class fenton catalyst
Effect.
Further, the mass concentration of calcium chloride solution is 3-6%, and the time of crosslinking curing is 2-12 hours, gel ball
Drying means any of can be dehydrated using vacuum dehydrating at lower temperature, freeze-drying, vacuum and low temperature oil bath.
Further, mixture and grinding media heap volume are according to 100g：200-600mL ratio adds mechanical activation solid phase
In reactor, carry out after ball-milling reaction, reaction 0.5-1.5h, stop in the case where rotating speed is 200-600rpm and 30-60 DEG C of constant temperature
Only heat and stir, separation product and abrading-ball obtain lignocellulosic ester admixture.
Further, cellulosic solid waste is that bagasse, cassava grain stillage, Cassava stalk, wood chip, bamboo scraps, stalk, ramulus mori are any
One or more kinds of combinations.
Further, cellulosic solid waste is dried, the requirement of crushing is：Water content is less than 15%, is crushed to 20-60 mesh.
Further, described mechanical activation solid phase reactor stirs for horizontal and/or verticle reinforced polysaccharide modified-high polymer
Mix ball-milling reaction device.
Described Horizontal reinforced polysaccharide polymer modification agitating ball mill reactor, agent structure includes agitating device, ball milling
Cylinder, mill ball, charging aperture, motor and the discharging opening being placed in ball grinding cylinder, described agitating device include the master being sequentially connected
Axle, feather key, spline fitting, U-shaped frame and the blades for transmitting moment of torsion, the master that described motor passes through transmission device and agitating device
Axle connects and drives U-shaped frame to radially wobble along main shaft, and described blades stirs mill ball under the drive of U-shaped frame and rolled in ball grinding cylinder
Dynamic, ball-milling reaction device also includes constant temperature system.
The verticle reinforced polysaccharide modified-high polymer stirring ball-milling reaction device, it is to be driven by drive device by shaft coupling
Agitating shaft, it also include cylinder cover plate, grinding inner cylinder, cooling jacket, liner plate, funneling material charging aperture, material discharging opening with
And mill ball, the stirrer paddle group equipped with inclined plate type blade and the spiral blade composition of S types, described on described agitating shaft
Inclined plate type blade is installed in parallel on agitating shaft, is arranged on above and below the described spiral blade of S types on agitating shaft；Described inclines
Ramp type blade is provided with some through holes for being available for grinding that mill ball passes through in inner cylinder；Described agitating shaft and the spiral blade of S types
It is hollow structure.Described grinding inner cylinder bottom is hemispherical.Described ball-milling reaction device is awarded from following two
Two patents of power：A kind of mechanical activation reactor .ZL 201420803894.3 for strengthening polysaccharide modified-high polymer；It is horizontal strong
Change polysaccharide modified-high polymer stirring ball-milling reaction device .ZL 201210466391.7.
Product after mechanical activation esterification modification, utilizes the activation one of mechanical force in mechanical activation course of reaction
Aspect can improve the content of lignocellulosic hydroxyl and phenolic hydroxyl group, on the other hand access carboxyl by esterification, tool
There is the ability of very strong Absorptive complex wave and chelates ferric ions, iron ion will not be lost in use.
The lignocellulosic ester group class fenton catalyst obtained present invention also offers the above method is in terms of wastewater treatment
Application.
The english abbreviation of sodium alginate is NaAlg, and the english abbreviation of sodium alginate solidification bead is Alg, lignocellulosic
The english abbreviation of ester is LCE.
Lignocellulosic ester-sodium alginate, abbreviation LCE-NaAlg, after immobilization have been obtained in the blended liquid of the present invention
Obtain lignocellulosic ester/sodium alginate solidification bead abbreviation LCE-Alg.
In the prior art, conventional GPC ball balling-up mechanism is as follows：Sodium alginate (NaAlg) is macromolecular substances, and surface is taken
The hydrophilic functional groups such as band carboxyl, are dissolved in after water, stronger hydrogen bond network can be formed between NaAlg and hydrone, is made
Strong hydration occurs for NaAlg macromoleculars, causes the gelation of solution.NaAlg solution is instilled into CaCl2In solution, NaAlg
Drop is rapidly and Ca2+Reaction is crosslinked, the curing molding under the supporting role of hydrone of the Alg beads after crosslinking.After drying,
Hydrone volatilizees, and produces hole.Carried out because cross-linking reaction is ecto-entad, react the most abundant and successively inside on top layer
Successively decrease so that Alg bead internal layer hydrones are more.Therefore during drying, the mesh-structured son that dries out of crosslinking
Supporting role and collapse, and the small outer surface of ball of dried Alg is close, internal sparse layering, there is larger space.
In the present invention, forming method, the process for obtaining gel ball are different from conventional method, specific as follows：
Lignocellulosic ester (LCE) can form new hydrogen bond network structure during with the mixing of NaAlg solution, make
NaAlg is covered in LCE surfaces, and adhesive effect is produced to adjacent LCE, and scattered LCE in the solution assembles in this role.
LCE and NaAlg mixed liquor is instilled into CaCl2In solution, because LCE is insoluble, and wrapped up by NaAlg molecules, therefore mainly
By NaAlg and Ca2+Reaction is crosslinked, while the curing molding under hydrone and LCE supporting role.And LCE addition,
The mesh of crosslinking can be made to diminish, and low-moisture gasification temperature can effectively drop in LCE and NaAlg interaction, dry
During, beneficial to the volatilization of hydrone, and then produce small hole.Further, since LCE supporting role, the LCE- after solidification
Alg beads can't be deformed upon because son is dried out, and can keep good spherical structure and mechanical strength.
The present invention has the beneficial effect that：
1st, there are the functional groups such as substantial amounts of hydroxyl, phenolic hydroxyl group, carboxyl on products obtained therefrom surface, with catalysis, active oxidation agent
Function；The organic matter in waste water can be adsorbed in these functional groups, oxidative degradation is carried out in catalyst surface, effectively increase
Degradation effect；
2nd, the iron ion/ferrous ion loaded in product can produce Fenton effect, and with organic official of lignocellulosic ester
It can roll into a ball and produce synergy, energy catalytic oxidant produces the hydroxyl radical free radical or peroxy radical of strong oxidizing property, the organic dirt of acceleration
Contaminate the degraded of thing；
3rd, prepared interiors of products is loose structure, and specific surface area and pore capacities are big, and specific surface area is 3~5m2/ g,
Absorption pore volume is 6~10cm3/ mg, the specific surface area than the lignocellulosic ester of not balling-up improves more than 50%, can be more effective
The useless Organic substance in water of absorption carries out oxidative degradation；
4th, sodium alginate has substantial amounts of carboxylic group, is acted synergistically with lignocellulosic ester, iron ion formation, improves catalysis
Efficiency；
5th, product is free of heavy metal, is not in the secondary pollution of leaching ability of heavy metal institute band, applied to catalysis organic wastewater
Oxidative degradation can be carried out at ambient pressure, it is only necessary to the oxidative degradation device with stirring, easy to operate.Particularly apply existing
Original handling process is varied without during Waste Water Treatment, can directly be applied；
6th, the high mechanical strength of this product, reusable more than 10 times；
7th, turned waste into wealth with cellulosic solid waste etc. for raw material, the treatment of wastes with processes of wastes against one another, realize cellulosic solid waste recycling,
Higher value application.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can various modifications may be made or changes to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Following examples 1-11 be different condition under prepare catalyst
Embodiment 1
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：Bagasse fibre matter solid waste drying to water content is less than 5%, crushing and obtained 40 mesh
The cellulosic solid waste powder of sieve；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (citric acid) and ferrous salt (FeSO4) press 100:
20:5 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:400mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 500rpm and 50 DEG C of water bath with thermostatic control, reach
After the 1.0h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 1% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 4 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 3%2In solution, crosslinking curing 2h, gel ball freeze-drying obtains specific surface area 4.6156m2/ g, absorption pore volume
9.135cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 2
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：Manioc waste cellulosic solid waste drying to water content is less than 8%, crushing and obtained 20 mesh
The cellulosic solid waste powder of sieve；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (butanedioic acid) and ferrous salt (FeCl2) press 100:
15:1 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:250mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 450rpm and 40 DEG C of water bath with thermostatic control, reach
After the 1.5h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 2% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 6 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 5%2In solution, crosslinking curing 10h, gel ball freeze-drying obtains specific surface area 4.0273m2/ g, adsorption hole
Hold 8.026cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 3
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：Ramulus mori cellulosic solid waste drying to water content is less than 15%, crushing and obtained 30 mesh sieves
Cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (maleic acid) and ferrous salt (Fe (NO3)2) press 100:
10:2 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:200mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 400rpm and 30 DEG C of water bath with thermostatic control, reach
After the 1.2h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 5% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 8 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 4%2In solution, crosslinking curing 6h, gel ball freeze-drying obtains specific surface area 3.8674m2/ g, absorption pore volume
7.633cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 4
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：Cassava grain stillage cellulosic solid waste drying to water content is less than 8%, crushing and obtained 45
The cellulosic solid waste powder of mesh sieve；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (butene dioic acid) and molysite (Fe (NO3)3) press 100:
5:2 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:500mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 200rpm and 60 DEG C of water bath with thermostatic control, reach
After the 0.8h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 3% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 5 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 6%2In solution, crosslinking curing 11h, gel ball vacuum dehydrating at lower temperature obtains specific surface area 3.1827m2/ g, suction
Attached pore volume 6.356cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 5
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：Cassava stalk cellulosic solid waste drying to water content is less than 10%, crushing and obtained 25 mesh
The cellulosic solid waste powder of sieve；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (glutaconate, malic acid are mixed) and molysite (Fe2
(SO4)3) press 100:25:8 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:400mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 500rpm and 50 DEG C of water bath with thermostatic control, reach
After the 0.8h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 5% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 7 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 4%2In solution, crosslinking curing 9h, gel ball vacuum dehydrating at lower temperature obtains specific surface area 3.4465m2/ g, absorption
Pore volume 7.013cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 6
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：Wood chip rod fibers matter solid waste drying to water content is less than 7%, crushing and obtained 50 mesh
The cellulosic solid waste powder of sieve；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (amino acid, citric acid are mixed) and molysite (FeCl3)
By 100：8：3 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:600mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 450rpm and 35 DEG C of water bath with thermostatic control, reach
After the 0.5h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 2% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 5 in sodium solution：1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 5%2In solution, crosslinking curing 11h, gel ball vacuum dehydrating at lower temperature obtains specific surface area 3.2524m2/ g, suction
Attached pore volume 6.832cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 7
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：Bamboo scraps rod fibers matter solid waste drying to water content is less than 12%, crushing and obtained 35 mesh
The cellulosic solid waste powder of sieve；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (suberic acid, malonic acid, maleic acid are mixed) and ferrous iron
Salt (FeCl2、Fe(NO3)2Mixing) press 100:30:6 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:450mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 400rpm and 40 DEG C of water bath with thermostatic control, reach
After the 1.0h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 4% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 7 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 4%2In solution, crosslinking curing 7h, gel ball vacuum dehydrating at lower temperature obtains specific surface area 4.8546m2/ g, absorption
Pore volume 9.695cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 8
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：Straw fiber matter solid waste drying to water content is less than 10%, crushing and obtained 40 mesh sieves
Cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (glutaric acid, glutaconate are mixed) and molysite
(FeCl3、Fe(NO3)3、Fe2(SO4)3Mixing) press 100:22:7 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:400mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 350rpm and 55 DEG C of water bath with thermostatic control, reach
After the 1.3h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 3% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 5 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 3%2In solution, crosslinking curing 10h, gel ball vacuum and low temperature oil bath is dehydrated, and obtains specific surface area
4.4238m2/ g, absorption pore volume 9.015cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 9
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：By bagasse, cassava grain stillage mix the drying of cellulosic solid waste to water content be less than 8%,
Crush the cellulosic solid waste powder for obtaining 30 mesh sieves；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (adipic acid, pimelic acid, maleic acid are mixed) and molysite
(Fe(NO3)3、Fe2(SO4)3Mixing) press 100:16:5 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:350mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 400rpm and 50 DEG C of water bath with thermostatic control, reach
After the 1.5h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 4% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 6 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 4%2In solution, crosslinking curing 5h, gel ball vacuum and low temperature oil bath is dehydrated, and obtains specific surface area
4.8236m2/ g, absorption pore volume 9.704cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 10
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：The cellulosic solid waste drying that wood chip, bamboo scraps, stalk are mixed is to water content 10%, powder
The broken cellulosic solid waste powder for obtaining 35 mesh sieves；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent (oxalic acid, malonic acid, amino acid, citric acid are mixed)
And ferrous salt (Fe (NO3)2、Fe2(SO4)2Mixing) press 100:13:3 ratio is added to mixer and is well mixed, and is mixed
Thing；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:500mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 500rpm and 40 DEG C of water bath with thermostatic control, reach
After the 0.6h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 2% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 5 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 3%2In solution, crosslinking curing 12h, gel ball vacuum dehydrating at lower temperature obtains specific surface area 4.3783m2/ g, suction
Attached pore volume 8.521cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Embodiment 11
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method bag
Include following steps：
(1) pretreatment of raw material：The cellulosic solid waste drying that bagasse, stalk, ramulus mori are mixed is to water content 10%, powder
The broken cellulosic solid waste powder for obtaining 40 mesh sieves；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent, (adipic acid, butene dioic acid, amino acid, malic acid are mixed
Close) and molysite (Fe (NO3)3、Fe2(SO4)3Mixing) press 100:25:7 ratio is added to mixer and is well mixed, and is mixed
Thing；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:350mL ratio adds
Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 550rpm and 35 DEG C of water bath with thermostatic control, reach
After the 1.3h reaction time, stop stirring, separation esterification products and abrading-ball, obtain lignocellulosic ester admixture；
(4) curing molding：Lignocellulosic ester admixture is added to the alginic acid of mass concentration 3% under conditions of stirring
(mass ratio of lignocellulosic ester admixture and sodium alginate is 6 in sodium solution:1) blended liquid, is obtained, blended liquid instills quality
The CaCl of concentration 4%2In solution, crosslinking curing 10h, gel ball vacuum and low temperature oil bath is dehydrated, and obtains specific surface area
4.4254m2/ g, absorption pore volume 8.639cm3/ mg lignocellulosic ester/sodium alginate composite catalyst.
Above-mentioned catalyst is applied to the experimental verification of various wastewater treatments
Embodiment 12
Application of the lignocellulosic ester/sodium alginate complex spherical class fenton catalyst in catalytic oxidation treatment paper waste
Lignocellulosic ester/sea prepared by embodiment 1 is added in initial COD concentration is 3500mg/L paper waste
The quality that mosanom complex spherical class fenton catalyst and oxidant (hydrogen peroxide), catalyst and oxidant are added is respectively waste water
The 1.0% of quality and 2.5%, it is that 9.0, reaction temperature is to occur redox reaction, reaction time under the conditions of 30 DEG C in pH value
90min, COD clearance reach 96%, and colourity removal efficiency reaches 94%.Catalyst is repeatable to be utilized 12 times.
Embodiment 13
Lignocellulosic ester/sodium alginate complex spherical class fenton catalyst is in catalytic oxidation treatment azo dyeing waste water
Using
Lignocellulosic ester/sea prepared by embodiment 5 is added in initial concentration is 180mg/L azo dyeing waste water
The quality that mosanom complex spherical class fenton catalyst and oxidant (hydrogen peroxide), catalyst and oxidant are added is respectively waste water
The 0.5% of quality and 2.0%, it is that 7.0, reaction temperature is to occur redox reaction, reaction time under the conditions of 45 DEG C in pH value
60min, Dye Wastewater Decolorization removal efficiency reaches more than 99%, and dyestuff is mineralized as CO2、H2O、N2Etc. harmless small-molecule substance, mineralization rate
Reach more than 93%.Catalyst is repeatable to be utilized 21 times.
Embodiment 14
Lignocellulosic ester/sodium alginate complex spherical class fenton catalyst is in catalytic oxidation treatment hydroquinones Industry Waste
The application of water
The lignocellulosic prepared by embodiment 8 is added in initial concentration is 200mg/L hydroquinones industrial wastewater
The quality difference that ester/sodium alginate complex spherical class fenton catalyst and oxidant (hydrogen peroxide), catalyst and oxidant are added
0.8% for wastewater quality and 1.5%, is that 4.0, reaction temperature is to occur redox reaction under the conditions of 60 DEG C in pH value, instead
120min between seasonable, hydroquinones is mineralized as CO2And H2O, mineralization rate reaches more than 90%.Catalyst is repeatable to be utilized 17 times.
Above-described embodiment 12-14 has excellent treatment effect to various waste water, repeats utilization rate high, it is contemplated that
It is that other target products in embodiment 1-11 are all effective to various wastewater treatments, and the present invention is not just repeated one by one.
In addition, the mechanical strength on product of the present invention, applicant takes qualitative analysis, succinctly it is described as follows：Arbitrarily
The close sample of 5 particle diameters is chosen, places it between two pieces of smooth glass plates, counterweight is added on a glass, is passed through
Observe the deformed condition of immobilized spherule, the mechanical strength of qualitative analysis adsorbing sphere.
By comparing under target product bead and other products on the market, equivalent weight counterweight, the deformation of product of the present invention
It is significantly less than like product, this also provides guarantee for the reuse of target product.
Claims (10)
1. the preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, it is characterised in that including as follows
Step：
Cellulosic solid waste is dried, crushed, and obtains cellulosic solid waste powder；
Cellulosic solid waste powder, esterifying agent, molysite and/or ferrous salt, are well mixed, obtain mixture；
Mixture is added in mechanical activation solid phase reactor, and ball milling simultaneously carries out esterification, separation esterification products and abrading-ball, is obtained
Lignocellulosic ester admixture；
Lignocellulosic ester admixture is added in sodium alginate soln under conditions of stirring, obtains blended liquid；
Blended liquid is instilled in calcium chloride solution, crosslinking curing, filtering, and gel ball solidified, load iron is dried, produced
Target product lignocellulosic ester/sodium alginate complex spherical class fenton catalyst.
2. preparation method according to claim 1, it is characterised in that cellulosic solid waste powder：Esterifying agent：Molysite and/
Or ferrous salt=100：5-30：1-8, mass ratio.
3. according to any described preparation methods of claim 1-2, it is characterised in that lignocellulosic ester admixture and alginic acid
The mass ratio of sodium is 4-8：1, the mass concentration of sodium alginate soln is 1-5%.
4. preparation method according to claim 3, it is characterised in that the esterifying agent includes oxalic acid, malonic acid, amber
Acid, glutaric acid, adipic acid, pimelic acid, suberic acid, maleic acid, butene dioic acid, glutaconate, malic acid, amino acid, citric acid
Any of or two or more combinations.
5. preparation method according to claim 3, it is characterised in that the molysite is FeCl3、Fe(NO3)3、Fe2(SO4)3
Any of or two or more combinations, the ferrous salt be FeCl2、Fe(NO3)2、FeSO4Any of or two kinds with
On combination.
6. the preparation method according to claim 4 or 5, it is characterised in that the mass concentration of calcium chloride solution is 3-6%,
The time of crosslinking curing is 2-12 hours, and the drying means of gel ball can be low using vacuum dehydrating at lower temperature, freeze-drying, vacuum
Warm oil bath any of is dehydrated.
7. according to any described preparation methods of claim 1-2, it is characterised in that mixture and grinding media heap volume according to
100g：200-600mL ratio is added in mechanical activation solid phase reactor, is 200-600rpm and 30-60 DEG C of constant temperature in rotating speed
Under the conditions of carry out ball-milling reaction, after reaction 0.5-1.5h, stop heating and stir, separation product and abrading-ball obtain wood fibre
Plain ester admixture.
8. preparation method according to claim 1, it is characterised in that described cellulosic solid waste is bagasse, cassava
Vinasse, Cassava stalk, wood chip, bamboo scraps, stalk, ramulus mori any one or two or more combinations.
9. preparation method according to claim 8, it is characterised in that cellulosic solid waste is dried, the requirement of crushing is：Contain
Water is less than 15%, is crushed to 20-60 mesh.
10. the lignocellulosic ester that the preparation method as described in claim 1-9 is any is obtained/sodium alginate complex spherical class is fragrant
The application of catalyst in the treatment of waste water.
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| CN110615518A (en) * | 2019-05-07 | 2019-12-27 | 中冶华天工程技术有限公司 | Fenton reaction ferrous iron slow release granule |
| CN111204896A (en) * | 2020-01-15 | 2020-05-29 | 国网山东省电力公司电力科学研究院 | Desulfurization wastewater pretreatment process based on flocculation-Fenton-like coupling method and activating agent |
| CN111233225A (en) * | 2020-01-16 | 2020-06-05 | 深圳市蓝清环境科技工程有限公司 | UV-FENTON wastewater treatment process |
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| CN104646062A (en) * | 2015-02-12 | 2015-05-27 | 浙江理工大学 | Preparation method for bamboo pulp cellulose-based integrated Fenton catalyst Fe<3+>C2O4/R |
| CN105399963A (en) * | 2015-12-17 | 2016-03-16 | 广西大学 | Mechanical-activation solid-phase preparation method of lignocellulose ester group oxidation catalyst |
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| WO2014099441A1 (en) * | 2012-12-18 | 2014-06-26 | E.I. Du Pont De Nemours And Company | Method for enhanced recovery of oil from oil reservoirs |
| CN104646062A (en) * | 2015-02-12 | 2015-05-27 | 浙江理工大学 | Preparation method for bamboo pulp cellulose-based integrated Fenton catalyst Fe<3+>C2O4/R |
| CN105399963A (en) * | 2015-12-17 | 2016-03-16 | 广西大学 | Mechanical-activation solid-phase preparation method of lignocellulose ester group oxidation catalyst |
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| CN110615518A (en) * | 2019-05-07 | 2019-12-27 | 中冶华天工程技术有限公司 | Fenton reaction ferrous iron slow release granule |
| CN110615518B (en) * | 2019-05-07 | 2022-05-24 | 中冶华天工程技术有限公司 | Fenton reaction ferrous iron slow release granule |
| CN111204896A (en) * | 2020-01-15 | 2020-05-29 | 国网山东省电力公司电力科学研究院 | Desulfurization wastewater pretreatment process based on flocculation-Fenton-like coupling method and activating agent |
| CN111233225A (en) * | 2020-01-16 | 2020-06-05 | 深圳市蓝清环境科技工程有限公司 | UV-FENTON wastewater treatment process |
| CN111233225B (en) * | 2020-01-16 | 2022-03-08 | 深圳市蓝清环境科技工程有限公司 | UV-FENTON wastewater treatment process |
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