CN107321384B - Lignocellulosic ester/sodium alginate complex spherical class fenton catalyst preparation method and applications - Google Patents
Lignocellulosic ester/sodium alginate complex spherical class fenton catalyst preparation method and applications Download PDFInfo
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- CN107321384B CN107321384B CN201710498150.3A CN201710498150A CN107321384B CN 107321384 B CN107321384 B CN 107321384B CN 201710498150 A CN201710498150 A CN 201710498150A CN 107321384 B CN107321384 B CN 107321384B
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- 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
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 56
- 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 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002910 solid waste Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000004137 mechanical activation Methods 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 9
- 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 34
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 18
- 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
- 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 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-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
- 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 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
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000004043 dyeing Methods 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
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-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
- 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
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-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
- 239000010842 industrial wastewater Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000010893 paper waste Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 229920002522 Wood fibre Polymers 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 238000011282 treatment Methods 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 28
- 238000002156 mixing Methods 0.000 description 17
- 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
- 238000003746 solid phase reaction Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 9
- 241001330002 Bambuseae Species 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 238000012545 processing Methods 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
- 238000001179 sorption measurement Methods 0.000 description 6
- -1 which adds Chemical compound 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000463 material Substances 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
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006731 degradation reaction 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
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 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
- 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
- 238000005516 engineering process Methods 0.000 description 3
- 229910001447 ferric ion Inorganic materials 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
- 238000006479 redox reaction Methods 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
- 238000010521 absorption reaction Methods 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
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen 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
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 241001474374 Blennius Species 0.000 description 1
- 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
- 230000004913 activation Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005284 basis set Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution 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
- 239000010410 layer Substances 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
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 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
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
-
- B01J35/612—
-
- B01J35/638—
-
- 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
Abstract
The present invention provides lignocellulosic ester/sodium alginate complex spherical class fenton catalyst preparation methods, are applied to field of waste water treatment.This method is first dry by cellulosic solid waste, crushes, obtain cellulosic solid waste powder, it is uniformly mixed again with esterifying agent, molysite and/or ferrous salt, it is added in mechanical activation solid phase reactor, ball milling simultaneously carries out esterification, esterification products and abrading-ball is separated, after obtaining lignocellulosic ester admixture, it is added in sodium alginate soln under stirring conditions, obtains blended liquid；Blended liquid instills in calcium chloride solution, crosslinking curing, filtering, obtains cured, load iron gel ball, dry to get 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, it realizes that recycling, the higher value application of cellulosic solid waste, products therefrom can generate Fenton effect, and is porous structure, water treatment effect is excellent, without secondary pollution, and reusable rate is high.
Description
Technical field
The invention belongs to field of waste water treatment, are related to lignocellulosic and are modified, specifically lignocellulosic ester/seaweed
The preparation method and applications of sour sodium complex spherical class fenton catalyst.
Background technique
With chemical industry and its high speed development of related industry, especially chemical industry, pesticide, 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 of national one third or more to be contaminated, and 90%
Above urban waters 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 the organic pollutant of these difficult for biological degradation has that the time is long, migration circle is wide, processing in water
Difficulty is big, increasingly serious to the harm of ecological environment and human health, and traditional processing technique is difficult to meet higher and higher ring
Guaranteed request.Therefore, exploitation is efficiently, economic technology is used to handle difficult for biological degradation, highly toxic organic pollutant wastewater has been compeled
In the eyebrows and eyelashes.High-level oxidation technology is a kind of New Wastewater Treatment Technology art, extremely strong using the activity generated in chemical reaction process
Free radical (such as OH, HO2Deng) organic pollutant macromolecular is made to be degraded to low toxicity or nontoxic small molecule, or even directly
Mineralising is water and carbon dioxide.Achieve the effect that deep oxidation is degraded, needs efficient oxidation catalyst.It is currently used to urge
Agent contains heavy metal more, is easy residual in the solution, and catalyst is difficult to biodegrade after, causes secondary pollution, and
Require pH value that high therefore complicated for operation, processing cost is higher.
Industrial organic waste water difficult to degrade is handled at present mainly uses Fenton (Fenton) oxidation technology, but Fenton oxidation
System still has following deficiency in use:
1, Fenton handles large labor intensity: hydrogen peroxide operation difficulty is big, and it must be solid that ferrous sulfate, which adds, and sulfuric acid is sub-
Iron iron content 20% or so considerably increases Treatment of Sludge intensity relative to 11% iron content of Polyferric Sulfate；
2, Fenton processing is at high cost, and sludge is more: the oxidation of hydrogen peroxide, which cannot give full play to, keeps reagent cost higher,
And ferrous sulfate adds bring amount sludge, processing cost it is high (present most enterprises cost calculated toward contact not
Increase including sludge), in addition there are equipment depreciation, maintenance costs etc.；
3, Fenton processing is easy to return color: as the dosage of hydrogen peroxide and ferrous sulfate and the ratio that adds control bad or three
Valence iron, which does not precipitate, to be easy to cause that treated aqueous solution shows yellowish or yellowish-brown；
4, Fenton processing corrosivity is big: hydrogen peroxide has strong oxidizing property, and oxidisability is only second to fluorine gas, can aoxidize equipment
Corrosion, if protection is bad to have a degree of corrosion to human body；
5, it can not reuse.
The Chinese invention patent application of Publication No. CN104646062A, 2015 applying date February 12nd, publication date
On May 27th, 2015, a kind of bamboo pulp fiber element basis set was described into fenton catalyst Fe3+C2O4The preparation method of/R, main points are
It is coordinated ferric iron and oxalic acid to form complex compound Fe3+C2O4/ R, then it is carried on the bamboo pulp fiber element synthesized by bamboo pulpboard
On base porous resin R, integrated fenton catalyst Fe is formed3+C2O4/ R can accelerate catalyzing hydrogen peroxide to degrade under visible light
Dye class organic pollutant in dyeing waste water.The patent application does not disclose how it carries out wastewater treatment and place in embodiment
The data result of reason can not learn its effect.
Publication No. CN105289527A Chinese invention patent application, December 03 2015 applying date, publication date 2016
In on February 03, 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, carries out esterification modification to cellulose and prepares cellulose esters, cellulose esters is dissolved in certain solvent, then is passed through
Cellulose esters aeroge adsorbent material is prepared in solvent reclamation exchange.This method is non-solid phase reaction, using compared with multi-solvent.
China has lignocellulosic sources abundant, and southern each province is especially prominent, source such as sugarcane, cassava, sawdust, 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 circular economy political affairs
Plan has important practical significance
Summary 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.
Concrete scheme of the invention is as follows:
Cellulosic solid waste is dry, crushes, and obtains cellulosic solid waste powder；
Cellulosic solid waste powder, esterifying agent, molysite and/or ferrous salt are uniformly mixed, obtain mixture；
Mixture is added in mechanical activation solid phase reactor, and ball milling simultaneously carries out esterification, separates esterification products and abrading-ball,
Obtain lignocellulosic ester admixture；
Lignocellulosic ester admixture is added in sodium alginate soln under stirring conditions, obtains blended liquid；
Blended liquid instills in calcium chloride solution, crosslinking curing, and filtering obtains cured, load iron gel ball, dry,
Up to 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, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, horse
Come any one of sour, butene dioic acid, glutaconate, malic acid, amino acid, citric acid or two or more combinations.Esterifying agent
Esterification occurs with cellulosic solid waste.
Further, the molysite is FeCl3、Fe(NO3)3、Fe2(SO4)3Any one of or two or more combinations,
The ferrous salt is FeCl2、Fe(NO3)2、FeSO4Any one of or two or more combinations, the effect of molysite or ferrous salt
There are two aspects, first is that the esterification of catalysis lignocellulosic plays class fenton catalyst second is that being carried on target product
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 can using vacuum dehydrating at lower temperature, freeze-drying, vacuum and low temperature oil bath dehydration and drying any one of.
Further, mechanical activation solid phase is added according to the ratio of 100g:200-600mL in mixture and grinding media heap volume
In reactor, ball-milling reaction is carried out in the case where revolving speed is 200-600rpm and 30-60 DEG C of constant temperature, after reacting 0.5-1.5h, is stopped
Only heating and stirring, separation product and abrading-ball obtain lignocellulosic ester admixture.
Further, cellulosic solid waste is that bagasse, cassava grain stillage, Cassava stalk, sawdust, bamboo scraps, stalk, ramulus mori are any
A combination of one or more.
Further, the requirement that cellulosic solid waste is dry, crushes are as follows: water content is crushed to 20-60 mesh less than 15%.
Further, the mechanical activation solid phase reactor is that horizontal and/or verticle reinforced polysaccharide modified-high polymer stirs
Mix ball-milling reaction device.
The Horizontal reinforced polysaccharide polymer modification agitating ball mill reactor, main structure include agitating device, ball milling
Cylinder, mill ball, feed inlet, motor and the discharge port being placed in ball grinding cylinder, the agitating device includes sequentially connected master
Axis, feather key, spline fitting, U-shaped frame and the blades for transmitting torque, the motor pass through the master of transmission device and agitating device
Axis connection simultaneously drives U-shaped frame to radially wobble along main shaft, and blades agitation mill ball under the drive of U-shaped frame rolls in ball grinding cylinder
Dynamic, ball-milling reaction device further includes constant temperature system.
The verticle reinforced polysaccharide modified-high polymer stirring ball-milling reaction device, it is to be driven by driving device by shaft coupling
Agitating shaft, it further include cylinder cover board, grinding inner cylinder, cooling jacket, liner plate, funneling material feed inlet, material discharge port with
And mill ball, the stirrer paddle group on the agitating shaft equipped with inclined plate type blade and the spiral blade composition of S type are described
Inclined plate type blade is installed in parallel on agitating shaft, and the spiral blade of S type is mounted on agitating shaft up and down；Described inclines
Ramp type blade is equipped with several through-holes passed through for mill ball in grinding inner cylinder；The agitating shaft and the spiral blade of S type
It is hollow structure.The grinding inner cylinder bottom is hemispherical.The ball-milling reaction device is awarded from following two
A kind of two patents of power: mechanical activation reactor .ZL 201420803894.3 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 reaction process
The content of lignocellulosic hydroxyl and phenolic hydroxyl group can be improved in aspect, on the other hand accessed 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 present invention also provides lignocellulosic ester group class fenton catalysts obtained by the above method in terms of wastewater treatment
Application.
The english abbreviation of sodium alginate is NaAlg, and the english abbreviation that sodium alginate solidifies bead is Alg, lignocellulosic
The english abbreviation of ester is LCE.
Lignocellulosic ester-sodium alginate, abbreviation LCE-NaAlg, after immobilization have been obtained in blended liquid of the 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, after being dissolved in water, can form stronger hydrogen bond network between NaAlg and hydrone, make
Strong hydration occurs for NaAlg macromolecular, causes the gelation of solution.NaAlg solution is instilled into CaCl2In solution, NaAlg liquid
Drop is rapidly and Ca2+Reaction is crosslinked, the curing molding under the supporting role of hydrone of the Alg bead after crosslinking.After drying, water
Molecule volatilization, generates hole.Because cross-linking reaction is that ecto-entad carries out, react the most abundant on surface layer, and successively inwardly pass
Subtract, so that Alg bead internal layer hydrone is more.Therefore during drying, the branch of the mesh-structured son that dries out of crosslinking
Support is acted on and is collapsed, and the small outer surface of ball of Alg after drying is close, and the sparse layering in inside, there are larger gaps.
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 on the surface LCE, generates adhesive effect to adjacent LCE, the LCE dispersed in the solution assembles in this role.It will
The mixed liquor of LCE and NaAlg instills CaCl2In solution, because of LCE insoluble, and wrapped up by NaAlg molecule, thus mainly according to
By NaAlg and Ca2+Crosslink reaction, while the curing molding under the supporting role of hydrone and LCE.And the addition of LCE, energy
The mesh of crosslinking is enough set to become smaller, and the interaction of LCE and NaAlg can effectively reduce the gasification temperature of moisture, in dry mistake
Cheng Zhong conducive to the volatilization of hydrone, and then generates small hole.Further, since the supporting role of LCE, the LCE-Alg after solidification
Bead can't because dry out son and deformation occurs, be able to maintain good spherical structure and mechanical strength.
The present invention has the beneficial effect that:
1, there are the functional groups such as a large amount of hydroxyl, phenolic hydroxyl group, carboxyl on products obtained therefrom surface, has catalysis, active oxidation agent
Function；The organic matter in waste water can be adsorbed in these functional groups, carry out oxidative degradation in catalyst surface, effectively increase
Degradation effect；
2, the iron ion/ferrous ion loaded in product can generate Fenton effect, and organic official with lignocellulosic ester
It can roll into a ball and generate synergistic effect, energy catalytic oxidant generates the hydroxyl radical free radical or peroxy radical of strong oxidizing property, accelerates organic dirt
Contaminate the degradation of object；
3, prepared interiors of products is porous structure, and specific surface area and pore capacities are big, and specific surface area is 3~5m2/ g inhales
Attached 6~10cm of Kong Rongwei3/ mg, the specific surface area than the lignocellulosic ester of not balling-up improve 50% or more, can more effectively adsorb
Useless Organic substance in water carries out oxidative degradation；
4, sodium alginate has a large amount of carboxylic group, is formed and is acted synergistically with lignocellulosic ester, iron ion, improves catalysis
Efficiency；
5, product is free of heavy metal, is not in the secondary pollution of heavy metal dissolution institute's band, is applied to catalysis organic wastewater
Oxidative degradation can carry out under normal pressure, it is only necessary to the oxidative degradation device with stirring, it is easy to operate.It especially applies existing
Original treatment process is varied without when waste water treatment system, can directly be applied；
6, the high mechanical strength of this product, reusable 10 times or more；
7, turned waste into wealth with cellulosic solid waste etc. for raw material, the treatment of wastes with processes of wastes against one another, the recycling of realization cellulosic solid waste,
Higher value application.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can various modifications may be made or change, such equivalent forms equally fall within the application the appended claims and limited to the present invention
Range.
Following examples 1-11 is to prepare catalyst under different condition
Embodiment 1
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) 40 mesh pretreatment of raw material: are obtained less than 5%, crushing in bagasse fibre matter solid waste drying to water content
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 mixing machine and is uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:400mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 500rpm and 50 DEG C of water bath with thermostatic control, reach
After the 1.0h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 4:1), 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, adsorption hole hold
9.135cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 2
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) 20 mesh pretreatment of raw material: are obtained less than 8%, crushing in manioc waste cellulosic solid waste drying to water content
The cellulosic solid waste powder of sieve；
(2) mixed at high speed: by cellulosic solid waste powder, esterifying agent (succinic acid) and ferrous salt (FeCl2) press 100:15:
1 ratio is added to mixing machine and is uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:250mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 450rpm and 40 DEG C of water bath with thermostatic control, reach
After the 1.5h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 6:1), 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 8.026cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 3
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) 30 meshes pretreatment of raw material: are obtained less than 15%, crushing in ramulus mori cellulosic solid waste drying to water content
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:
The ratio of 10:2 is added to mixing machine and is uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:200mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 400rpm and 30 DEG C of water bath with thermostatic control, reach
After the 1.2h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 8:1), 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, adsorption hole hold
7.633cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 4
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) cassava grain stillage cellulosic solid waste drying to water content pretreatment of raw material: is obtained 45 less than 8%, crushing
The cellulosic solid waste powder of mesh；
(2) mixed at high speed: by cellulosic solid waste powder, esterifying agent (butene dioic acid) and molysite (Fe (NO3)3) press 100:
The ratio of 5:2 is added to mixing machine and is uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:500mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 200rpm and 60 DEG C of water bath with thermostatic control, reach
After the 0.8h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 5:1), 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 hole holds 6.356cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 5
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) 25 mesh pretreatment of raw material: are obtained less than 10%, crushing in Cassava stalk cellulosic solid waste drying to water content
The cellulosic solid waste powder of sieve；
(2) mixed at high speed: by cellulosic solid waste powder, esterifying agent (glutaconate, malic acid mix) and molysite (Fe2
(SO4)3) in the ratio of 100:25:8 be added to mixing machine be uniformly mixed, obtain mixture；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:400mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 500rpm and 50 DEG C of water bath with thermostatic control, reach
After the 0.8h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 7:1), 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
Hole holds 7.013cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 6
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) 50 mesh pretreatment of raw material: are obtained less than 7%, crushing in sawdust rod fibers matter solid waste drying to water content
The cellulosic solid waste powder of sieve；
(2) mixed at high speed: by cellulosic solid waste powder, esterifying agent (amino acid, citric acid mix) and molysite (FeCl3)
Mixing machine is added in the ratio of 100:8:3 to be uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:600mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 450rpm and 35 DEG C of water bath with thermostatic control, reach
After the 0.5h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 5:1), 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 hole holds 6.832cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 7
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) 35 mesh pretreatment of raw material: are obtained less than 12%, crushing in bamboo scraps rod fibers matter solid waste drying to water content
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 mix) and ferrous iron
Salt (FeCl2、Fe(NO3)2Mixing) in the ratio of 100:30:6 be added to mixing machine be uniformly mixed, obtain mixture；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:450mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 400rpm and 40 DEG C of water bath with thermostatic control, reach
After the 1.0h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 7:1), 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
Hole holds 9.695cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 8
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) 40 meshes pretreatment of raw material: are obtained less than 10%, crushing in straw fiber matter solid waste drying to water content
Cellulosic solid waste powder；
(2) mixed at high speed: by cellulosic solid waste powder, esterifying agent (glutaric acid, glutaconate mix) and molysite
(FeCl3、Fe(NO3)3、Fe2(SO4)3Mixing) in the ratio of 100:22:7 be added to mixing machine be uniformly mixed, obtain mixture；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:400mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 350rpm and 55 DEG C of water bath with thermostatic control, reach
After the 1.3h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 5:1), 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 dehydration and drying obtains specific surface area
4.4238m2/ g, adsorption hole hold 9.015cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 9
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) pretreatment of raw material: the cellulosic solid waste that bagasse, cassava grain stillage are mixed it is dry to water content less than 8%,
Crush the cellulosic solid waste powder that 30 meshes are obtained；
(2) mixed at high speed: by cellulosic solid waste powder, esterifying agent (adipic acid, pimelic acid, maleic acid mix) and molysite
(Fe(NO3)3、Fe2(SO4)3Mixing) in the ratio of 100:16:5 be added to mixing machine be uniformly mixed, obtain mixture；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:350mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 400rpm and 50 DEG C of water bath with thermostatic control, reach
After the 1.5h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 6:1), 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 dehydration and drying obtains specific surface area
4.8236m2/ g, adsorption hole hold 9.704cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 10
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) pretreatment of raw material: the cellulosic solid waste that sawdust, bamboo scraps, stalk are mixed is dry to water content 10%, crushing
The cellulosic solid waste powder of 35 meshes is obtained；
(2) mixed at high speed: by cellulosic solid waste powder, esterifying agent (oxalic acid, malonic acid, amino acid, citric acid mix)
And ferrous salt (Fe (NO3)2、Fe2(SO4)2Mixing) in the ratio of 100:13:3 be added to mixing machine be uniformly mixed, mixed
Object；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:500mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 500rpm and 40 DEG C of water bath with thermostatic control, reach
After the 0.6h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 5:1), 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 hole holds 8.521cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
Embodiment 11
A kind of preparation method of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst, the preparation method packet
Include following steps:
(1) pretreatment of raw material: the cellulosic solid waste that bagasse, stalk, ramulus mori are mixed is dry to water content 10%, powder
The broken cellulosic solid waste powder that 40 meshes are obtained；
(2) mixed at high speed: by cellulosic solid waste powder, esterifying agent (adipic acid, butene dioic acid, amino acid, apple acid-mixed
Close) and molysite (Fe (NO3)3、Fe2(SO4)3Mixing) in the ratio of 100:25:7 be added to mixing machine be uniformly mixed, mixed
Object；
(3) mechanical activation solid phase reaction: said mixture and grinding media heap volume are added according to the ratio of 100g:350mL
Enter in mechanical activation solid phase reactor, carries out ball-milling reaction at a temperature of revolving speed is 550rpm and 35 DEG C of water bath with thermostatic control, reach
After the 1.3h reaction time, stop stirring, separates 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 stirring conditions
In sodium solution (mass ratio of lignocellulosic ester admixture and sodium alginate is 6:1), 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 dehydration and drying obtains specific surface area
4.4254m2/ g, adsorption hole hold 8.639cm3Lignocellulosic ester/sodium alginate composite catalyst of/mg.
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 the paper waste that initial COD concentration is 3500mg/L
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%, redox reaction, reaction time occurs under the conditions of pH value is 9.0, reaction temperature is 30 DEG C
90min, COD removal rate reach 96%, and coloration removal efficiency reaches 94%.Catalyst reusable 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 the azo dyeing waste water that initial concentration is 180mg/L
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%, redox reaction, reaction time occurs under the conditions of pH value is 7.0, reaction temperature is 45 DEG C
60min, Dye Wastewater Decolorization removal efficiency reach 99% or more, and dyestuff is mineralized as CO2、H2O、N2Etc. harmless small-molecule substance, mineralization rate
Reach 93% or more.Catalyst reusable 21 times.
Embodiment 14
Lignocellulosic ester/sodium alginate complex spherical class fenton catalyst is in catalytic oxidation treatment hydroquinone Industry Waste
The application of water
Lignocellulosic prepared by embodiment 8 is added in the hydroquinone industrial wastewater that initial concentration is 200mg/L
The quality difference that ester/sodium alginate complex spherical class fenton catalyst and oxidant (hydrogen peroxide), catalyst and oxidant are added
It is the 0.8% of wastewater quality and 1.5%, redox reaction occurs under the conditions of pH value is 4.0, reaction temperature is 60 DEG C, instead
120min between seasonable, hydroquinone are mineralized as CO2And H2O, mineralization rate reach 90% or more.Catalyst reusable 17 times.
Above-described embodiment 12-14 has excellent treatment effect to various waste water, and reusable rate is high, it is contemplated that
It is that other target products in embodiment 1-11 are all effectively that the present invention does not just repeat one by one to various wastewater treatments.
In addition, the mechanical strength about product of the present invention, applicant takes qualitative analysis, is succinctly described as follows: any
Sample similar in 5 partial sizes is chosen, is placed it between two pieces of smooth glass plates, is added counterweight on a glass, pass through
Observe the deformed condition of immobilized spherule, the mechanical strength of qualitative analysis adsorbing sphere.
By comparing target product bead and other products on the market, under equivalent weight counterweight, the deformation of product of the present invention
It is significantly less than similar product, this also provides guarantee for the reuse of target product.
Claims (10)
1. lignocellulosic ester/sodium alginate complex spherical class fenton catalyst preparation method, which is characterized in that including as follows
Step:
Cellulosic solid waste is dry, crushes, and obtains cellulosic solid waste powder；
Cellulosic solid waste powder, esterifying agent, molysite and/or ferrous salt are uniformly mixed, obtain mixture；
Mixture is added in mechanical activation solid phase reactor, and ball milling simultaneously carries out esterification, separates esterification products and abrading-ball, obtains
Lignocellulosic ester admixture；
Lignocellulosic ester admixture is added in sodium alginate soln under stirring conditions, obtains blended liquid；
Blended liquid instills in calcium chloride solution, crosslinking curing, and filtering obtains cured, load iron gel ball, it is dry to get
Target product lignocellulosic ester/sodium alginate complex spherical class fenton catalyst.
2. preparation method according to claim 1, which is characterized in that cellulosic solid waste powder: esterifying agent: molysite and/
Or the mass ratio of ferrous salt is 100:5-30:1-8.
3. preparation method according to claim 1 to 2, which is characterized in that lignocellulosic ester admixture and alginic acid
The mass ratio of sodium is 4-8:1, and the mass concentration of sodium alginate soln is 1-5%.
4. preparation method according to claim 3, which is characterized 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 one of or two or more combinations.
5. preparation method according to claim 3, which is characterized in that the molysite is FeCl3、Fe(NO3)3、Fe2(SO4)3
Any one of or two or more combinations, the ferrous salt be FeCl2、Fe(NO3)2、FeSO4Any one of or two kinds with
On combination.
6. preparation method according to claim 4 or 5, which is characterized 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 is using vacuum dehydrating at lower temperature, freeze-drying, vacuum and low temperature oil
Any one of bath dehydration and drying.
7. preparation method according to claim 1 to 2, which is characterized in that mixture and grinding media heap volume according to
The ratio of 100g:200-600mL is added in mechanical activation solid phase reactor, is 200-600rpm and 30-60 DEG C of constant temperature in revolving speed
Under the conditions of carry out ball-milling reaction, after reacting 0.5-1.5h, stop heating and stirring, separation product and abrading-ball, obtain wood fibre
Plain ester admixture.
8. preparation method according to claim 1, which is characterized in that the cellulosic solid waste is bagasse, cassava
Vinasse, Cassava stalk, sawdust, bamboo scraps, stalk, ramulus mori any one or two or more combinations.
9. preparation method according to claim 8, which is characterized in that cellulosic solid waste is dry, the requirement that crushes are as follows: contains
Water is crushed to 20-60 mesh less than 15%.
10. the lignocellulosic ester that the preparation method as described in claim 1-9 is any obtains/sodium alginate complex spherical class is fragrant
Application of the catalyst in paper waste, azo dyeing waste water, hydroquinone Industrial Wastewater Treatment.
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