CN104646062A - Preparation method for bamboo pulp cellulose-based integrated Fenton catalyst Fe<3+>C2O4/R - Google Patents
Preparation method for bamboo pulp cellulose-based integrated Fenton catalyst Fe<3+>C2O4/R Download PDFInfo
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 80
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 80
- 241001330002 Bambuseae Species 0.000 title claims abstract description 80
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 80
- 239000011425 bamboo Substances 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 229920002678 cellulose Polymers 0.000 title claims abstract description 19
- 239000001913 cellulose Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000835 fiber Substances 0.000 claims description 32
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005284 basis set Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 241000196324 Embryophyta Species 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000008236 heating water Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 240000005827 Phyllostachys nigra Species 0.000 claims description 4
- 235000010717 Phyllostachys nigra Nutrition 0.000 claims description 4
- 240000002014 Phyllostachys nigra var. henonis Species 0.000 claims description 3
- 240000003096 Chimonobambusa quadrangularis Species 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 38
- 238000000034 method Methods 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000012028 Fenton's reagent Substances 0.000 abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- 235000006408 oxalic acid Nutrition 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 238000004043 dyeing Methods 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 230000001133 acceleration Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 210000000630 fibrocyte Anatomy 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
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- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
The invention discloses a preparation method for a bamboo pulp cellulose-based integrated Fenton catalyst Fe<3+>C2O4/R. The preparation method is characterized in that tri-valent iron and oxalic acid are subjected to coordination to form a complex Fe<3+>C2O4, and the complex Fe<3+>C2O4 is loaded on bamboo pulp cellulose-based porous resin R synthesized by bamboo pulp to form the integrated Fenton catalyst Fe<3+>C2O4/R; under visible light, hydrogen peroxide can be catalyzed in an acceleration manner to degrade dye type organic pollutants in printing and dyeing wastewater. A product prepared by the method is high in efficiency, environment-friendly and low in cost; the problems of secondary pollution, high oxidization cost, low degrading efficiency and the like which are caused by a fact that the Fenton reagent cannot be repeatedly used in the conventional dye type organic pollutant Fenton oxidization degrading are solved, and the creation concept of using bamboo resources in China in a high value is provided, and thus the preparation method has obvious environmental and social significance.
Description
Technical field
The present invention relates to a kind of preparation method of integrated fenton catalyst, particularly a kind of bamboo pulp fiber element basis set becomes fenton catalyst Fe
3+c
2o
4the preparation method of/R, belongs to high-molecular organic material technical field.
Background technology
Fenton oxidation is one of important technology of advanced treatment of industrial waste water, is to utilize hydrogen peroxide, with ferrous strong oxidizing property, oxidation operation is become inorganic states, reaches the object of degradation of organic waste water.During organic pollution, there is Fenton reagent and can not reuse and then cause secondary pollution in tradition Fenton oxidation, the limitations such as oxidation cost is high, degradation efficiency is low in degrading waste water.In recent years, the light of iron or iron complex is utilized to help hardly degraded organic substance in multiphase-fenton Fenton degradation water to cause the extensive concern of researcher.In early-stage Study, although add oxalic acid can improve catalytic efficiency, catalyst is not recyclable and then cause oxidation cost high.Simple load class heterogeneous catalyst can realize reclaiming, but reaction rate is in reduced levels always, is dropped into industrial imagination and is difficult to realize.
Its characteristic of technical scheme that we propose at this is, utilizes cellulose base porous resin load ferric oxalate on the one hand, realizes ferric iron Catalyzed by Oxalic Acid agent complex compound Fe
3+c
2o
4the recovery and reuse of/R, thus the processing cost reducing process Fenton oxidation, and minimizing flowing molten iron loses the secondary environmental pollution caused; On the other hand making part with iron forms ferric iron Catalyzed by Oxalic Acid agent complex compound by adding the oxalates with light sensitivity, can improve the defects such as the reaction rate caused due to heterogeneous catalyst is low, raising multiphase-fenton Fenton is degraded the speed of dyeing waste water and efficiency.In the preparation of multiphase-fenton fenton catalyst and application thereof, Chinese patent (CN201410465387) " surface-modified nano tri-iron tetroxide fenton catalyst and preparation method thereof " prepares high dispersancy nano tri-iron tetroxide by coprecipitation, then carries out surface modification by Hydrolyze method to nano ferriferrous oxide; Chinese patent (CN201410483397) " a kind of method preparing heterogeneous light Fenton catalyst " is by goethite-Graphene-mesoporous supports material triplicity, for the excellent catalytic effect of organic pollutants (particularly phenol, nitrogen heterocyclic ring etc.), pH is applied widely, repeat performance is good, effectively can reduce COD and TOC in waste water simultaneously; Chinese patent (CN201410448550) " a kind of take molecular sieve as heterogeneous fenton catalyst of Fe-Mn bimetallic of carrier and its preparation method and application " is by MnSO
4h
2o and FeSO
47H
2obtain mixed system after the mixing of O solution, in mixed system, add NaY molecular sieve, mix, in above-mentioned mixed system, add citric acid, water-bath, gained dope is dried, calcine, obtain the heterogeneous fenton catalyst of Fe-Mn/NaY support type; United States Patent (USP) (US 20060138057 A1) " Eco-friendly photo
- fenton catalyst-immobilized Fe (III) over HY-zeolite " ferric ion is fixed on HY zeolite through methods such as dipping, calcinings obtains isomery iron (III)-HY catalyst; by evaluating its catalyst activity to the Fenton degraded of phenolic waste liquor, and study iron load capacity, H
2o
2concentration, the factors such as pH value are on the impact of catalyst light Fenton's reaction; United States Patent (USP) (US 20050274678 A1) " Integrated technology in sequential treatment of organics and heavy metal ions wastewater " provides a kind of integrated technology for the continuous complicated wastewater treatment process containing low biological degradability organic matter and heavy metal ion produced by process of surface treatment, is conducive to the ferrite quality reducing Fenton oxidation process iron mud generation and improve processing procedure generation.So far, yet there are no and utilize bamboo pulp fiber element as molecular skeleton matrix, become the related process technologies of fenton catalyst to occur in order to prepare bamboo pulp fiber element basis set.
Meanwhile, China is the country studying, cultivate and utilize bamboo in the world the earliest, and bamboo resource is very abundant, the important sources of bamboo Ye Shi China bamboo district peasant economy income.Bamboo belongs to rank vegetation resource, has fast growth, the cycle of becoming a useful person is short, fiber content advantages of higher, and fibre morphology and fibrocyte content are close to even higher than general leaf wood.Make full use of the bamboo resource of China's abundant, the renewable new material of preparation high added value, opens one's minds, meets national development circular economy policy, have important practical significance for one that becomes higher value application China bamboo resource.
Summary of the invention
In order to overcome in traditional Fenton oxidation process industrial wastewater process, Fenton reagent is difficult to reclaim and then cause secondary pollution, the problems such as oxidation cost is high, degradation efficiency is low, the bamboo resource of recycling China's abundant prepares the renewable new material of high added value simultaneously, the object of this invention is to provide a kind of bamboo pulp fiber element basis set and becomes fenton catalyst Fe
3+c
2o
4the preparation method of/R.
For achieving the above object, technical scheme of the present invention adopts following steps:
1) plant pulverizer is adopted to pulverize bamboo pulpboard, filter through 100 eye mesh screens, obtain particle diameter and be less than or equal to 0.15 mm bamboo pulp powder, add alkaline solution vigorous stirring 2 ~ 4 min of precooling to-10 ~-25 DEG C, leave standstill reaction 60 ~ 120 min, taking-up is placed in ice bath and stirs, and obtains the bamboo pulp fiber cellulose solution of homogeneous transparent;
2) under mechanical agitation, bamboo pulp fiber cellulose solution heating water bath to 50 ~ 70 DEG C that step 1) is obtained, pass into nitrogen 20 ~ 40 min, the ammonium persulfate adding 0.1 ~ 0.2 g/g bamboo pulp powder causes 10 ~ 20 min, add the acrylamide of 0.5 ~ 1.0 g/g bamboo pulp powder successively, the acrylic acid of 2.0 ~ 4.0 g/g bamboo pulp powder and the N-N '-methylene-bisacrylamide through NaOH neutralization of 15 ~ 25 mg/g bamboo pulp powder, continue logical nitrogen reaction 1 ~ 3 h, product deionized water is washed till neutrality, add absolute ethyl alcohol dehydration 12 ~ 24 h, freeze drying obtains bamboo pulp fiber element base porous resin R,
3) by 0.1 ~ 0.2 mol/L Na
2c
2o
4with Fe (NO
3)
3solution respectively gets 10 mL hybrid reaction 20 ~ 40 min, by 40 ~ 60 mg steps 2) bamboo pulp fiber that obtains element base porous resin R adds above-mentioned mixed solution, reaction 24 h is shaken under 20 ~ 40 DEG C, water bath with thermostatic control oscillator, 100 ~ 120 r/min conditions, product deionized water is washed till neutrality, and namely vacuum drying obtains integrated fenton catalyst Fe
3+c
2o
4/ R product.
Described alkaline solution is NaOH and urea mixed solution, wherein the mass percent of NaOH, urea and deionized water is respectively 4 ~ 6 wt%, 9 ~ 11 wt% and 83 ~ 87 wt%, and bamboo pulp powder carries out mixing and reacting with 2 g: 50 ~ 70 mL with this mixed solution.
Described bamboo pulpboard is the one in black bamboo pulpboard, square bamboo pulp plate, mao bamboon pulpboard and henon bamboo pulpboard.
Compared with background technology, the beneficial effect that the present invention has is:
The present invention introduces bamboo resource in the raw material of the integrated fenton catalyst of synthesis, has expanded the raw material range of the integrated fenton catalyst of preparation; The bamboo pulp fiber element basis set of preparing of the present invention's proposition becomes fenton catalyst Fe
3+c
2o
4the method of/R is conducive to solving in traditional Fenton oxidation degraded dyeing waste water dye class organic pollution process, Fenton reagent can not reuse and then cause secondary pollution, the problems such as oxidation cost is high, degradation efficiency is low, propose opening one's minds of higher value application China bamboo resource simultaneously, meet national development circular economy policy, be expected to the income conscientiously improving China bamboo district peasant.
Accompanying drawing explanation
Fig. 1 is integrated fenton catalyst Fe prepared by embodiment 1
3+c
2o
4the field emission scanning electron microscope photo of/R product.Wherein, Fig. 1 a is that cellulose base porous resin amplifies 10,000 times of photos, and Fig. 1 b is integrated fenton catalyst Fe
3+c
2o
4/ R amplifies 5,000 times of photos.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
embodiment 1:
1) plant pulverizer is adopted to pulverize henon bamboo pulpboard, filter through 100 eye mesh screens, obtain particle diameter and be less than or equal to 0.15 mm bamboo pulp powder, add alkaline solution vigorous stirring 4 min of precooling to-10 DEG C, leave standstill reaction 120 min, wherein alkaline solution is NaOH and urea mixed solution, the mass percent of NaOH, urea and deionized water is respectively 6 wt%, 11 wt% and 83 wt%, bamboo pulp powder carries out mixing and reacting with 2 g: 70 mL with mixed solution, then take out and be placed in ice bath and stir, obtain homogeneous transparent bamboo pulp fiber cellulose solution;
2) under mechanical agitation, the bamboo pulp fiber cellulose solution heating water bath to 70 DEG C that step 1) is obtained, pass into nitrogen 20 min, the ammonium persulfate adding 0.1 g/g bamboo pulp powder causes 20 min, add the acrylamide of 0.5 g/g bamboo pulp powder successively, the acrylic acid of 2.0 g/g bamboo pulp powder and the N-N '-methylene-bisacrylamide through NaOH neutralization of 15 mg/g bamboo pulp powder, continue logical nitrogen and react 1 h, product deionized water is washed till neutrality, add absolute ethyl alcohol to dewater 12 h, freeze drying obtains bamboo pulp fiber element base porous resin R;
3) by 0.1 mol/L Na
2c
2o
4with Fe (NO
3)
3solution respectively gets 10 mL hybrid reaction 20 min, by 40 mg steps 2) bamboo pulp fiber that obtains element base porous resin R adds above-mentioned mixed solution, reaction 24 h is shaken under 40 DEG C, water bath with thermostatic control oscillator, 100 r/min conditions, product deionized water is washed till neutrality, and namely vacuum drying obtains integrated fenton catalyst Fe
3+c
2o
4/ R product (a).
embodiment 2:
1) plant pulverizer is adopted to pulverize black bamboo pulpboard, filter through 100 eye mesh screens, obtain particle diameter and be less than or equal to 0.15 mm bamboo pulp powder, add alkaline solution vigorous stirring 3 min of precooling to-15 DEG C, leave standstill reaction 90 min, wherein alkaline solution is NaOH and urea mixed solution, the mass percent of NaOH, urea and deionized water is respectively 5 wt%, 10 wt% and 85 wt%, bamboo pulp powder carries out mixing and reacting with 2 g: 60 mL with mixed solution, then take out and be placed in ice bath and stir, obtain homogeneous transparent bamboo pulp fiber cellulose solution;
2) under mechanical agitation, the bamboo pulp fiber cellulose solution heating water bath to 60 DEG C that step 1) is obtained, pass into nitrogen 30 min, the ammonium persulfate adding 0.15 g/g bamboo pulp powder causes 15 min, add the acrylamide of 0.75 g/g bamboo pulp powder successively, the acrylic acid of 3.0 g/g bamboo pulp powder and the N-N '-methylene-bisacrylamide through NaOH neutralization of 20 mg/g bamboo pulp powder, continue logical nitrogen and react 2 h, product deionized water is washed till neutrality, add absolute ethyl alcohol to dewater 18 h, freeze drying obtains bamboo pulp fiber element base porous resin R;
3) by 0.15 mol/L Na
2c
2o
4with Fe (NO
3)
3solution respectively gets 10 mL hybrid reaction 30 min, by 50 mg steps 2) bamboo pulp fiber that obtains element base porous resin R adds above-mentioned mixed solution, reaction 24 h is shaken under 30 DEG C, water bath with thermostatic control oscillator, 110 r/min conditions, product deionized water is washed till neutrality, and namely vacuum drying obtains integrated fenton catalyst Fe
3+c
2o
4/ R product (b).
embodiment 3:
1) plant pulverizer is adopted to pulverize black bamboo pulpboard, filter through 100 eye mesh screens, obtain particle diameter and be less than or equal to 0.15 mm bamboo pulp powder, add alkaline solution vigorous stirring 2 min of precooling to-25 DEG C, leave standstill reaction 60 min, wherein alkaline solution is NaOH and urea mixed solution, the mass percent of NaOH, urea and deionized water is respectively 4 wt%, 9 wt% and 87 wt%, bamboo pulp powder carries out mixing and reacting with 2 g: 50 mL with mixed solution, then take out and be placed in ice bath and stir, obtain homogeneous transparent bamboo pulp fiber cellulose solution;
2) under mechanical agitation, the bamboo pulp fiber cellulose solution heating water bath to 50 DEG C that step 1) is obtained, pass into nitrogen 40 min, the ammonium persulfate adding 0.2 g/g bamboo pulp powder causes 10 min, add the acrylamide of 1.0 g/g bamboo pulp powder successively, the acrylic acid of 4.0 g/g bamboo pulp powder and the N-N '-methylene-bisacrylamide through NaOH neutralization of 25 mg/g bamboo pulp powder, continue logical nitrogen and react 3 h, product deionized water is washed till neutrality, add absolute ethyl alcohol to dewater 24 h, freeze drying obtains bamboo pulp fiber element base porous resin R;
3) by 0.2 mol/L Na
2c
2o
4with Fe (NO
3)
3solution respectively gets 10 mL hybrid reaction 40 min, by 60 mg steps 2) bamboo pulp fiber that obtains element base porous resin R adds above-mentioned mixed solution, reaction 24 h is shaken under 20 DEG C, water bath with thermostatic control oscillator, 120 r/min conditions, product deionized water is washed till neutrality, and namely vacuum drying obtains integrated fenton catalyst Fe
3+c
2o
4/ R product (c).
Measure water absorbent rate and the ferric iron load factor of the cellulose base porous resin R that embodiment 1,2,3 prepares.Table 1 is for being prepared the measurement result of ferric iron load factor on the water absorbent rate of cellulose base porous resin R, cellulose base porous resin R by embodiment 1,2,3.From data in table 1, a kind of bamboo pulp fiber element basis set of the present invention is adopted to become fenton catalyst Fe
3+c
2o
4integrated fenton catalyst Fe prepared by the preparation method of/R
3+c
2o
4/ R has higher ferric iron load factor.
As Fig. 1, from integrated fenton catalyst Fe prepared by embodiment 1
3+c
2o
4the field emission scanning electron microscope photo of/R product can be found out, it is loose porous that Fig. 1 a shows cellulose base porous resin pattern, is conducive to a large amount of loads of later stage ferric ion, and Fig. 1 b shows the integrated fenton catalyst Fe of preparation
3+c
2o
4its individual size of/R and specific area are suitable for, and are suitable for carrying out efficient light and help Fenton catalytic oxidation.
Table 1
What more than enumerate is only specific embodiments of the invention.The invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (3)
1. a bamboo pulp fiber element basis set becomes fenton catalyst Fe
3+c
2o
4the preparation method of/R, is characterized in that, comprises the following steps:
1) plant pulverizer is adopted to pulverize bamboo pulpboard, filter through 100 eye mesh screens, obtain particle diameter and be less than or equal to 0.15 mm bamboo pulp powder, add alkaline solution vigorous stirring 2 ~ 4 min of precooling to-10 ~-25 DEG C, leave standstill reaction 60 ~ 120 min, taking-up is placed in ice bath and stirs, and obtains the bamboo pulp fiber cellulose solution of homogeneous transparent;
2) under mechanical agitation, bamboo pulp fiber cellulose solution heating water bath to 50 ~ 70 DEG C that step 1) is obtained, pass into nitrogen 20 ~ 40 min, the ammonium persulfate adding 0.1 ~ 0.2 g/g bamboo pulp powder causes 10 ~ 20 min, add the acrylamide of 0.5 ~ 1.0 g/g bamboo pulp powder successively, the acrylic acid of 2.0 ~ 4.0 g/g bamboo pulp powder and the N-N '-methylene-bisacrylamide through NaOH neutralization of 15 ~ 25 mg/g bamboo pulp powder, continue logical nitrogen reaction 1 ~ 3 h, product deionized water is washed till neutrality, add absolute ethyl alcohol dehydration 12 ~ 24 h, freeze drying obtains bamboo pulp fiber element base porous resin R,
3) by 0.1 ~ 0.2 mol/L Na
2c
2o
4with Fe (NO
3)
3solution respectively gets 10 mL hybrid reaction 20 ~ 40 min, by 40 ~ 60 mg steps 2) bamboo pulp fiber that obtains element base porous resin R adds above-mentioned mixed solution, reaction 24 h is shaken under 20 ~ 40 DEG C, water bath with thermostatic control oscillator, 100 ~ 120 r/min conditions, product deionized water is washed till neutrality, and namely vacuum drying obtains integrated fenton catalyst Fe
3+c
2o
4/ R product.
2. a kind of bamboo pulp fiber element basis set according to claim 1 becomes fenton catalyst Fe
3+c
2o
4the preparation method of/R, it is characterized in that: described alkaline solution is NaOH and urea mixed solution, wherein the mass percent of NaOH, urea and deionized water is respectively 4 ~ 6 wt%, 9 ~ 11 wt% and 83 ~ 87 wt%, and bamboo pulp powder carries out mixing and reacting with 2 g: 50 ~ 70 mL with this mixed solution.
3. a kind of bamboo pulp fiber element basis set according to claim 1 becomes fenton catalyst Fe
3+c
2o
4the preparation method of/R, is characterized in that: described bamboo pulpboard is the one in black bamboo pulpboard, square bamboo pulp plate, mao bamboon pulpboard and henon bamboo pulpboard.
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105170183A (en) * | 2015-09-16 | 2015-12-23 | 天津工业大学 | Wool fiber metal complex photocatalyst and preparation method thereof |
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CN106219821A (en) * | 2016-08-30 | 2016-12-14 | 嘉兴赛维环保科技有限公司 | One utilizes cellulose base integrated Fenton catalyst Fe3+c2o4the method of/R advanced treatment of dyeing wastewater |
CN106587296A (en) * | 2016-11-28 | 2017-04-26 | 浙江理工大学 | Bamboo pulp cellulose based flocculation decolorization composite functional material and preparation method thereof |
CN106824996A (en) * | 2017-02-16 | 2017-06-13 | 广东工业大学 | A kind of method of smooth thermal coupling degradation biological matter discarded object |
CN107213916A (en) * | 2017-06-27 | 2017-09-29 | 广西大学 | The preparation method and applications of modified wood fibre element ester group class fenton catalyst |
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CN107321384A (en) * | 2017-06-27 | 2017-11-07 | 广西大学 | The preparation method and applications of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst |
CN110745982A (en) * | 2019-09-12 | 2020-02-04 | 生态环境部华南环境科学研究所 | Method for deep oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated monoperoxybisulfate |
CN113663737A (en) * | 2021-08-19 | 2021-11-19 | 南京医科大学康达学院 | CMC-Fe-based microsphere and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101660215A (en) * | 2009-09-23 | 2010-03-03 | 陈福库 | Protein and cellulose composite fiber and manufacturing method thereof |
CN102909073A (en) * | 2012-10-12 | 2013-02-06 | 浙江理工大学 | Preparation method and application of heterogeneous Fenton-like catalyst |
CN103406153A (en) * | 2013-07-29 | 2013-11-27 | 浙江理工大学 | Method for preparing cellulose-based macroporous gel compound Cu2O visible-light-driven photocatalyst |
KR20140013293A (en) * | 2012-07-23 | 2014-02-05 | 충남대학교산학협력단 | Manufacturing method of actived magnetite |
-
2015
- 2015-02-12 CN CN201510074499.5A patent/CN104646062A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101660215A (en) * | 2009-09-23 | 2010-03-03 | 陈福库 | Protein and cellulose composite fiber and manufacturing method thereof |
KR20140013293A (en) * | 2012-07-23 | 2014-02-05 | 충남대학교산학협력단 | Manufacturing method of actived magnetite |
CN102909073A (en) * | 2012-10-12 | 2013-02-06 | 浙江理工大学 | Preparation method and application of heterogeneous Fenton-like catalyst |
CN103406153A (en) * | 2013-07-29 | 2013-11-27 | 浙江理工大学 | Method for preparing cellulose-based macroporous gel compound Cu2O visible-light-driven photocatalyst |
Non-Patent Citations (2)
Title |
---|
HONGYI LIU等: "Flocculation characteristics of polyacrylamide grafted cellulose from Phyllostachys heterocycla: An efficient and eco-friendly flocculant", 《WATER RESEARCH》 * |
张瑛洁等: "树脂负载草酸铁光助类芬顿降解水中孔雀石绿", 《环境科学》 * |
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CN105170183A (en) * | 2015-09-16 | 2015-12-23 | 天津工业大学 | Wool fiber metal complex photocatalyst and preparation method thereof |
CN106006903A (en) * | 2016-05-27 | 2016-10-12 | 浙江理工大学 | Preparation method of bamboo-pulp cellulose and poly(N-vinylformamide) composite flocculating and decolorizing material |
CN106006903B (en) * | 2016-05-27 | 2018-12-18 | 浙江理工大学 | A kind of preparation method of bamboo pulp fiber element & polyvinylformamide composite flocculation decoloring material |
CN106219821A (en) * | 2016-08-30 | 2016-12-14 | 嘉兴赛维环保科技有限公司 | One utilizes cellulose base integrated Fenton catalyst Fe3+c2o4the method of/R advanced treatment of dyeing wastewater |
CN106587296A (en) * | 2016-11-28 | 2017-04-26 | 浙江理工大学 | Bamboo pulp cellulose based flocculation decolorization composite functional material and preparation method thereof |
CN106824996A (en) * | 2017-02-16 | 2017-06-13 | 广东工业大学 | A kind of method of smooth thermal coupling degradation biological matter discarded object |
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CN107321384A (en) * | 2017-06-27 | 2017-11-07 | 广西大学 | The preparation method and applications of lignocellulosic ester/sodium alginate complex spherical class fenton catalyst |
CN107213916A (en) * | 2017-06-27 | 2017-09-29 | 广西大学 | The preparation method and applications of modified wood fibre element ester group class fenton catalyst |
CN107233916B (en) * | 2017-06-27 | 2019-10-01 | 广西大学 | Carry the preparation method and applications of the cellulose ester-based spheric catalyst of hophornbeam matter |
CN110745982A (en) * | 2019-09-12 | 2020-02-04 | 生态环境部华南环境科学研究所 | Method for deep oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated monoperoxybisulfate |
CN113663737A (en) * | 2021-08-19 | 2021-11-19 | 南京医科大学康达学院 | CMC-Fe-based microsphere and preparation method and application thereof |
CN113663737B (en) * | 2021-08-19 | 2023-08-15 | 南京医科大学康达学院 | CMC-Fe-based microsphere, and preparation method and application thereof |
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