CN107213916A - The preparation method and applications of modified wood fibre element ester group class fenton catalyst - Google Patents

The preparation method and applications of modified wood fibre element ester group class fenton catalyst Download PDF

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Publication number
CN107213916A
CN107213916A CN201710498094.3A CN201710498094A CN107213916A CN 107213916 A CN107213916 A CN 107213916A CN 201710498094 A CN201710498094 A CN 201710498094A CN 107213916 A CN107213916 A CN 107213916A
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solid waste
wood fibre
acid
modified wood
preparation
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CN107213916B (en
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张燕娟
黄祖强
王雯
胡华宇
覃杏珍
杨梅
黄爱民
沈芳
冯振飞
覃宇奔
伍娟
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Guangxi University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • 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 invention provides the preparation method of the plain ester group class fenton catalyst of modified wood fibre, applied to field of waste water treatment.This method includes drying cellulosic solid waste, crushed, obtained cellulosic solid waste powder and modifying agent and auxiliary agent, it is well mixed, then mixture is added in mechanical activation solid phase reactor, ball milling is simultaneously reacted, separation product and abrading-ball, the obtained plain ester admixture of modified wood fibre is added under conditions of stirring in molysite and/or ferrous salt solution, filtering, filter residue passes through drying, produces target product.The present invention, for raw material, is turned waste into wealth, recycling, the higher value application of cellulosic solid waste are realized in the treatment of wastes with processes of wastes against one another with cellulosic solid waste etc., production process is solid phase method, simple to operate, and the modifying agent and auxiliary agent added is not required to be separated, there is no " three wastes ", low equipment investment, production cost is low；Products therefrom can produce Fenton effect, and water treatment efficiency is excellent, non-secondary pollution, and pH is wide using scope.

Description

The preparation method and applications of modified wood fibre element ester group class fenton catalyst
Technical field
The invention belongs to field of waste water treatment, it is related to lignocellulosic modification, specifically the plain ester of modified wood fibre The preparation method and applications of base class fenton catalyst.
Background technology
With chemical industry and its high speed development of related industry, especially chemical industry, agricultural chemicals, medicine, papermaking, printing and dyeing, smelting The development of the industries such as gold, a large amount of industrial wastewaters not standard discharge causes the section in the whole nation more than 1/3rd to be contaminated, and 90% Urban waters above are seriously polluted, and nearly 50% key cities water head site does not meet drinking water standard.Wherein, organic wastewater Type and quantity are increasing, and existence time length, migration circle are wide in water, handle for the organic pollution of these difficult for biological degradation Difficulty is big, and the harm to ecological environment and human health is increasingly serious, and traditional treatment technology is difficult to meet higher and higher ring Guaranteed request.Therefore, the technology developed efficiently, economic has been compeled for handling difficult for biological degradation, highly toxic organic pollutant wastewater In the eyebrows and eyelashes.High-level oxidation technology is a kind of New Wastewater Treatment Technology art, active extremely strong using what is produced in chemical reaction process Free radical (such as OH, HO2Deng) organic pollution macromolecular is degraded to low toxicity or nontoxic small molecule, or even directly Mineralising is connect for water and carbon dioxide.The effect of deep oxidation degraded is reached, it is necessary to efficient oxidation catalyst.Conventional at present Containing heavy metal catalyst, easily in the solution, catalyst is difficult to biodegradation to residual after, causes secondary pollution more, and And high is required to pH value, therefore complex operation, processing cost are higher.
Processing difficult degradation industrial organic waste water mainly uses Fenton (Fenton) oxidation technology, but Fenton oxygen at present There are still following not enough in use for change system：
1st, Fenton processing labor intensity is big：Hydrogen peroxide operation difficulty is big, and it must be solid that ferrous sulfate, which is added, and sulfuric acid is sub- Iron iron content 20% or so, relative to 11% iron content of Polyferric Sulfate, considerably increases Treatment of Sludge intensity；
2nd, the cost of Fenton processing is high, and sludge is more：The oxidation of hydrogen peroxide, which can not give full play to, makes reagent cost higher, And ferrous sulfate adds the amount sludge brought, processing cost it is high (cost that present most enterprises are calculated toward contact not Including sludge increase), in addition with equipment depreciation, maintenance cost etc.；
3rd, Fenton processing easily returns color：Dosage such as hydrogen peroxide and ferrous sulfate is bad with adding ratio control, or three Valency iron does not precipitate the aqueous solution being easily caused after processing and shows slightly yellow or yellowish-brown；
4th, Fenton processing corrosivity is big：Hydrogen peroxide has strong oxidizing property, and its oxidisability is only second to fluorine gas, can aoxidize equipment Corrosion, if protection is bad a certain degree of corrosion to human body；
5th, it can not reuse.
Publication No. CN104646062A Chinese invention patent application, the applying date 2015 year 02 month 12, publication date On 05 27th, 2015, a kind of plain basis set of bamboo pulp fiber was described into fenton catalyst Fe3+C2O4/ R preparation method, main points It is to be coordinated to form complex compound Fe by ferric iron and oxalic acid3+C2O4/ R, then it is carried on the bamboo pulp fiber synthesized by bamboo pulpboard On plain base porous resin R, integrated fenton catalyst Fe is formed3+C2O4/ R, can accelerate catalyzing hydrogen peroxide to drop under visible light Solve dye class organic pollution in dyeing waste water.The patent application do not disclosed in embodiment its how to carry out wastewater treatment and The data result of processing, it is impossible to learn its effect.
Publication No. CN105289527A Chinese invention patent applications, December 03 2015 applying date, publication date 2016 In 03 day 02 month year, a kind of preparation method of cellulose esters aerogel material is described, using cellulose as raw material, with long chain fatty acids Acyl chlorides is esterifying reagent, and carrying out esterification modification to cellulose prepares cellulose esters, and cellulose esters is dissolved in certain solvent, then is passed through Solvent reclamation exchanges and prepares cellulose esters aeroge sorbing material.This method is non-solid phase reaction, using compared with multi-solvent.
China has abundant lignocellulosic sources, and southern each province is especially prominent, source such as sugarcane, cassava, wood chip, bamboo Bits, stalk, ramulus mori etc..Resource is made full use of, the renewable new material of high added value is prepared, meets national development recycling economy political affairs Plan, has important practical significance.
The content of the invention
An object of the present invention be just to provide a kind of catalysis efficiency it is high, without heavy metal ion, simple production process and Lignocellulosic can be comprehensively utilized the catalyst of getting up, for handling waste water.
The concrete scheme of the present invention is as follows：
Cellulosic solid waste is dried, crushed, and obtains cellulosic solid waste powder；
Cellulosic solid waste powder, modifying agent and auxiliary agent, are well mixed, obtain mixture；
Mixture is added in mechanical activation solid phase reactor, and ball milling is simultaneously reacted, and separation product and abrading-ball are modified Lignocellulosic ester admixture；
The plain ester admixture of modified wood fibre is added under conditions of stirring in molysite and/or ferrous salt solution, mistake Filter, filter residue passes through drying, produces target product.
Further, above-described cellulosic solid waste powder：Modifying agent：Auxiliary agent=100：5-30：1-8, mass ratio.
As the further improvement of technical scheme, modifying agent described above include oxalic acid, malonic acid, butanedioic acid, glutaric acid, Adipic acid, pimelic acid, suberic acid, maleic acid, butene dioic acid, glutaconate, malic acid, amino acid, citric acid, ethylenediamine, two Any of isopropylamine, triethanolamine, diethylenetriamine, urea or two or more combinations.
As the further improvement of technical scheme, auxiliary agent described above is AlCl3、KNO3、Na2CO3、 Li2P2O7、 Na4P2O7、ZnCl2、MgCO3Any of or two or more combinations.
As the further improvement of technical scheme, molysite described above is FeCl3、Fe(NO3)3、Fe2(SO4)3In any Plant or two or more combinations, the ferrous salt is FeCl2、Fe(NO3)2、FeSO4Any of or two or more combinations.
As the further improvement of technical scheme, above molysite and/or ferrous salt solution total mass concentration are 2-10%.
As the further improvement of technical scheme, thing mixed above is with grinding media heap volume according to 100g： 200-600mL Ratio add in mechanical activation solid phase reactor, carry out ball milling in the case where rotating speed is 200-600rpm and 30-60 DEG C of constant temperature After reaction, reaction 0.5-1.5h, stop heating and stir, separation product and abrading-ball obtain the plain ester admixture of modified wood fibre.
As the further improvement of technical scheme, above cellulosic solid waste is dried, the requirement of crushing is：Water content is less than 15%, 20-60 mesh is crushed to, modified wood fibre element ester admixture is added to molysite and/or ferrous salt under conditions of stirring After in solution, refiltered after standing, time of repose is 0.5-24h.
As the further improvement of technical scheme, above-described cellulosic solid waste is bagasse, cassava grain stillage, cassava Bar, wood chip, bamboo scraps, stalk, ramulus mori any one or two or more combinations.
Modified wood fibre that above-described preparation method is obtained plain ester group class fenton catalyst is in the treatment of waste water Using.
Further, described mechanical activation solid phase reactor stirs for horizontal and/or verticle reinforced polysaccharide modified-high polymer Mix ball-milling reaction device.
Described Horizontal reinforced polysaccharide polymer modification agitating ball mill reactor, agent structure includes agitating device, ball milling Cylinder, mill ball, charging aperture, motor and the discharging opening being placed in ball grinding cylinder, described agitating device include the master being sequentially connected Axle, feather key, spline fitting, U-shaped frame and the blades for transmitting moment of torsion, the master that described motor passes through transmission device and agitating device Axle connects and drives U-shaped frame to radially wobble along main shaft, and described blades stirs mill ball under the drive of U-shaped frame and rolled in ball grinding cylinder Dynamic, ball-milling reaction device also includes constant temperature system.
The verticle reinforced polysaccharide modified-high polymer stirring ball-milling reaction device, it is to be driven by drive device by shaft coupling Agitating shaft, it also include cylinder cover plate, grinding inner cylinder, cooling jacket, liner plate, funneling material charging aperture, material discharging opening with And mill ball, the stirrer paddle group equipped with inclined plate type blade and the spiral blade composition of S types, described on described agitating shaft Inclined plate type blade is installed in parallel on agitating shaft, is arranged on above and below the described spiral blade of S types on agitating shaft；Described inclines Ramp type blade is provided with some through holes for being available for grinding that mill ball passes through in inner cylinder；Described agitating shaft and the spiral blade of S types It is hollow structure.Described grinding inner cylinder bottom is hemispherical.Described ball-milling reaction device is derived from that mandate is obtained as below Two patents：A kind of mechanical activation reactor .ZL 201420803894.3 for strengthening polysaccharide modified-high polymer；Horizontal reinforcing Polysaccharide modified-high polymer stirring ball-milling reaction device .ZL 201210466391.7.
By the modified product of mechanical activation, the activation one side of mechanical force in mechanical activation course of reaction is utilized Can improve the content of lignocellulosic hydroxyl and phenolic hydroxyl group, on the other hand by esterification and aminating reaction accessed carboxyl and Amido, the ability with very strong Absorptive complex wave and chelates ferric ions, in use iron ion will not be lost in.
The plain ester group class fenton catalyst of modified wood fibre obtained present invention also offers the above method is in wastewater treatment The application of aspect.
The present invention has the beneficial effect that：
1st, there are the functional groups such as substantial amounts of hydroxyl, phenolic hydroxyl group, carboxyl, amido on products obtained therefrom surface, with catalysis, active oxidation The function of agent；The organic matter in organic wastewater can be adsorbed in these functional groups, oxidative degradation is carried out in catalyst surface, have Effect improves degradation effect；
2nd, the iron ion loaded in product can produce Fenton effect, and be produced with the organo-functional group of the plain ester of modified wood fibre Raw synergy, energy catalytic oxidant produces the hydroxyl radical free radical or peroxy radical of strong oxidizing property, accelerates organic pollution Degraded；
3rd, pH in the range of 2-10 can effective catalytic oxidant, iron ion will not be lost in；
4th, production process is solid phase method, simple to operate, and the modifying agent and auxiliary agent added is not required to be separated, does not have " three It is useless ", low equipment investment, production cost is low；
5th, product is free of heavy metal, is not in the secondary pollution of leaching ability of heavy metal institute band, applied to catalysis organic wastewater Oxidative degradation can be carried out at ambient pressure, it is only necessary to the oxidative degradation device with stirring, easy to operate.Particularly apply existing Original handling process is varied without during Waste Water Treatment, can directly be applied；
6th, turned waste into wealth with cellulosic solid waste etc. for raw material, the treatment of wastes with processes of wastes against one another, realize cellulosic solid waste recycling, Higher value application.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art Member can various modifications may be made or changes to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Following examples 1-12 is the preparation of catalyst under different condition
Embodiment 1
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Bagasse fibre matter solid waste drying to water content is less than 10%, crushing and obtained 40 mesh The cellulosic solid waste powder of sieve；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent (citric acid) and auxiliary agent (AlCl3) press 100:6:1 Ratio be added to mixer be well mixed, obtain mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:350mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 400rpm and 40 DEG C of water bath with thermostatic control, reach After the 0.5h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By FeCl2It is dissolved in water, is prepared into the solution that mass concentration is 3%, modification is wooden Cellulose mixtures are slowly added into solution under conditions of stirring, are stood 0.5h after stirring, are filtrated to get and are loaded with The plain base class fenton catalyst of the modified wood fibre of iron ion, drying for standby.
Embodiment 2
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Manioc waste cellulosic solid waste drying to water content is less than 9%, crushing and obtained 35 mesh The cellulosic solid waste powder of sieve；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent (butanedioic acid) and auxiliary agent (ZnCl2) press 100:15:4 Ratio be added to mixer be well mixed, obtain mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:250mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 450rpm and 55 DEG C of water bath with thermostatic control, reach After the 0.6h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By FeCl2It is dissolved in water, is prepared into the solution that mass concentration is 4%, modification is wooden Cellulose mixtures are slowly added into solution under conditions of stirring, are stood 4h after stirring, are filtrated to get and are loaded with iron The plain base class fenton catalyst of the modified wood fibre of ion, drying for standby.
Embodiment 3
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Ramulus mori cellulosic solid waste drying to water content is less than 15%, crushing and obtained 20 mesh sieves Cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent (maleic acid, adipic acid are mixed with arbitrary proportion) and Auxiliary agent (ZnCl2) press 100:10:3 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:200mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 450rpm and 30 DEG C of water bath with thermostatic control, reach After the 1.0h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By FeCl3It is dissolved in water, is prepared into the solution that mass concentration is 2%, modification is wooden Cellulose mixtures are slowly added into solution under conditions of stirring, are stood 12h after stirring, are filtrated to get and are loaded with The plain base class fenton catalyst of the modified wood fibre of iron ion, drying for standby.
Embodiment 4
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Cassava grain stillage cellulosic solid waste drying to water content is less than 5%, crushing and obtained 30 The cellulosic solid waste powder of mesh sieve；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent, (malic acid, malonic acid, glutaconate are arbitrarily to compare Example mixing) and auxiliary agent (Li2P2O7) press 100:8:2 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:500mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 200rpm and 45 DEG C of water bath with thermostatic control, reach After the 1.5h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By Fe (NO3)2It is dissolved in water, the solution that mass concentration is 4% is prepared into, by innovation wood Matter cellulose mixtures are slowly added into solution under conditions of stirring, are stood 2h after stirring, are filtrated to get and are loaded with The plain base class fenton catalyst of the modified wood fibre of iron ion, drying for standby.
Embodiment 5
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Cassava stalk cellulosic solid waste drying to water content is less than 8%, crushing and obtained 25 mesh The cellulosic solid waste powder of sieve；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent (butene dioic acid) and auxiliary agent (Na4P2O7) press 100: 15:5 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:400mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 500rpm and 50 DEG C of water bath with thermostatic control, reach After the 1.2h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By FeSO4It is dissolved in water, is prepared into the solution that mass concentration is 5%, modification is wooden Cellulose mixtures are slowly added into solution under conditions of stirring, are stood 5h after stirring, are filtrated to get and are loaded with iron The plain base class fenton catalyst of the modified wood fibre of ion, drying for standby.
Embodiment 6
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Wood fiber matter solid waste drying to water content is less than 6%, crushing and obtained 60 mesh sieves Cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent (amino acid, oxalic acid are mixed with arbitrary proportion) and help Agent (MgCO3) press 100:12:4 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:600mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 450rpm and 60 DEG C of water bath with thermostatic control, reach After the 0.8h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By Fe (NO3)3It is dissolved in water, the solution that mass concentration is 6% is prepared into, by innovation wood Matter cellulose mixtures are slowly added into solution under conditions of stirring, are stood 24h after stirring, are filtrated to get and are loaded with The plain base class fenton catalyst of the modified wood fibre of iron ion, drying for standby.
Embodiment 7
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Bamboo scraps cellulosic solid waste drying to water content is less than 13%, crushing and obtained 35 mesh sieves Cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent (pimelic acid, maleic acid are mixed with arbitrary proportion) and Auxiliary agent (Na2CO3) press 100:20:7 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:450mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 350rpm and 55 DEG C of water bath with thermostatic control, reach After the 1.3h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By Fe2(SO4)3It is dissolved in water, the solution that mass concentration is 10% is prepared into, by modification Lignocellulosic mixture is slowly added into solution under conditions of stirring, and 18h is stood after stirring, and is filtrated to get negative It is loaded with the plain base class fenton catalyst of modified wood fibre of iron ion, drying for standby.
Embodiment 8
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Stalk fibre matter solid waste drying to water content is less than 7%, crushing and obtained 40 mesh sieves Cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent, (suberic acid, glutaric acid, glutaconate are arbitrarily to compare Example mixing) and auxiliary agent (KNO3) press 100:30:7 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:450mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 350rpm and 55 DEG C of water bath with thermostatic control, reach After the 1.3h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By Fe2(SO4)3It is dissolved in water, the solution that mass concentration is 8% is prepared into, by innovation wood Matter cellulose mixtures are slowly added into solution under conditions of stirring, and 16h is stood after stirring, and are filtrated to get load There are the plain base class fenton catalyst of modified wood fibre of iron ion, drying for standby.
Embodiment 9
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：The cellulosic solid waste drying that bagasse, Cassava stalk are mixed to water content is less than 5%, powder The broken cellulosic solid waste powder for obtaining 30 mesh sieves；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent (ethylenediamine) and auxiliary agent (AlCl3、 KNO3Mixing) press 100:8:3 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:350mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 400rpm and 50 DEG C of water bath with thermostatic control, reach After the 1.5h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By the FeCl of arbitrary proportion3、Fe(NO3)3It is dissolved in water, it is 7% to be prepared into mass concentration Solution, the plain mixture of modified wood fibre is slowly added into solution under conditions of stirring, stood after stirring 20h, is filtrated to get the plain base class fenton catalyst of modified wood fibre for being loaded with iron ion, drying for standby.
Embodiment 10
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：By cassava grain stillage, Cassava stalk mix the drying of cellulosic solid waste to water content be less than 7%, Crush the cellulosic solid waste powder for obtaining 25 mesh sieves；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent, (diisopropylamine, triethanolamine are mixed with arbitrary proportion Close) and auxiliary agent (Li2P2O7、Na4P2O7、Na2CO3Mixing) press 100:14:4 ratio is added to mixer and is well mixed, and is mixed Compound；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:300mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 500rpm and 60 DEG C of water bath with thermostatic control, reach After the 1.1h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By the FeCl of arbitrary proportion3、Fe(NO3)3、Fe2(SO4)3It is dissolved in water, is prepared into quality Concentration is 7% solution, and the plain mixture of modified wood fibre is slowly added into solution under conditions of stirring, stirred After stand 22h, be filtrated to get the plain base class fenton catalyst of modified wood fibre for being loaded with iron ion, drying for standby.
Embodiment 10
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：By wood chip, bamboo scraps, stalk mix the drying of cellulosic solid waste to water content be less than 12%, Crush the cellulosic solid waste powder for obtaining 35 mesh sieves；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent, (ethylenediamine, diethylenetriamine, urea are arbitrarily to compare Example mixing) and auxiliary agent (ZnCl2、MgCO3Mixing) press 100:25:7 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:500mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 300rpm and 40 DEG C of water bath with thermostatic control, reach After the 0.8h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By the FeCl of arbitrary proportion2、Fe(NO3)2It is dissolved in water, it is 3% to be prepared into mass concentration Solution, the plain mixture of modified wood fibre is slowly added into solution under conditions of stirring, 6h is stood after stirring, It is filtrated to get the plain base class fenton catalyst of modified wood fibre for being loaded with iron ion, drying for standby.
Embodiment 11
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Cellulosic solid waste drying to the water content that bagasse, stalk, ramulus mori are mixed is less than 10%th, the cellulosic solid waste powder for obtaining 40 mesh sieves is crushed；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent (citric acid, ethylenediamine are mixed with arbitrary proportion) and Auxiliary agent (AlCl3) press 100:12:3 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:400mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 500rpm and 50 DEG C of water bath with thermostatic control, reach After the 1.0h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By FeSO4It is dissolved in water, is prepared into the solution that mass concentration is 2%, modification is wooden Cellulose mixtures are slowly added into solution under conditions of stirring, are stood 10h after stirring, are filtrated to get and are loaded with The plain base class fenton catalyst of the modified wood fibre of iron ion, drying for standby.
Embodiment 12
A kind of preparation method of the plain base class fenton catalyst of modified wood fibre, the preparation method comprises the following steps：
(1) pretreatment of raw material：Cellulosic solid waste drying to the water content that bagasse, stalk, ramulus mori are mixed is less than 10%th, the cellulosic solid waste powder for obtaining 40 mesh sieves is crushed；
(2) mixed at high speed：By cellulosic solid waste powder, modifying agent, (butanedioic acid, maleic acid, triethanolamine are arbitrarily to compare Example mixing) and auxiliary agent (Na4P2O7) press 100:22:5 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture and grinding media heap volume according to 100g:300mL ratio adds Enter in mechanical activation solid phase reactor, carry out ball-milling reaction at a temperature of rotating speed is 550rpm and 30 DEG C of water bath with thermostatic control, reach After the 1.5h reaction time, stop stirring, separation product and abrading-ball, obtain the plain mixture of modified wood fibre；
(4) iron ion is loaded：By FeCl2It is dissolved in water, is prepared into the solution that mass concentration is 2%, modification is wooden Cellulose mixtures are slowly added into solution under conditions of stirring, are stood 3h after stirring, are filtrated to get and are loaded with iron The plain base class fenton catalyst of the modified wood fibre of ion, drying for standby.
Above-mentioned catalyst is applied to the experimental verification of various wastewater treatments
Embodiment 13
Application of the modified wood fibre element base class fenton catalyst in catalytic oxidation treatment paper waste
The modified wood fibre element prepared by embodiment 1 is added in initial COD concentration is 1500mg/L paper waste The quality that base class fenton catalyst and oxidant (hydrogen peroxide), catalyst and oxidant are added is respectively the 0.5% of wastewater quality It is that 10.0, reaction temperature is to occur redox reaction under the conditions of 40 DEG C in pH value, in reaction time 120min, COD is gone with 2% Except rate reaches 95%, colourity removal efficiency reaches 93%.
Embodiment 14
Application of the modified wood fibre element base class fenton catalyst in catalytic oxidation treatment dyeing waste water
The plain base class of modified wood fibre added in initial concentration is 80mg/L dyeing waste water prepared by embodiment 3 is fragrant Pause catalyst and oxidant (hydrogen peroxide), and the quality that catalyst and oxidant are added is respectively 0.3% He of wastewater quality 1.5%, it is that 7.0, reaction temperature is to occur redox reaction, reaction time 60min, Dye Wastewater Decolorization under the conditions of 50 DEG C in pH value Removal efficiency reaches more than 99%, and dyestuff is mineralized as CO2、H2O、N2Etc. harmless small-molecule substance, mineralization rate reaches more than 90%.
Embodiment 15
Application of the modified wood fibre element base class fenton catalyst in catalytic oxidation treatment phenol industrial wastewater
The modified wood fibre element prepared by embodiment 11 is added in initial concentration is 200mg/L phenol industrial wastewater The quality that base class fenton catalyst and oxidant (hydrogen peroxide), catalyst and oxidant are added is respectively the 0.8% of wastewater quality It is that 2.0, reaction temperature is to occur redox reaction, reaction time 90min, phenol quilt under the conditions of 60 DEG C in pH value with 1.2% Mineralising is CO2And H2O, mineralization rate reaches more than 85%.
Above-described embodiment 13-15 has excellent treatment effect to various waste water, it is anticipated that embodiment 1-12 In other target products be all to various wastewater treatments it is effective, the present invention just do not repeat one by one.

Claims (10)

1. the preparation method of modified wood fibre element ester group class fenton catalyst, it is characterised in that comprise the following steps：
Cellulosic solid waste is dried, crushed, and obtains cellulosic solid waste powder；
Cellulosic solid waste powder, modifying agent and auxiliary agent, are well mixed, obtain mixture；
Mixture is added in mechanical activation solid phase reactor, and ball milling is simultaneously reacted, separation product and abrading-ball, obtains being modified wooden Cellulose ester mixture；
The plain ester admixture of modified wood fibre is added under conditions of stirring in molysite and/or ferrous salt solution, filtered, filter Slag passes through drying, produces target product.
2. preparation method according to claim 1, it is characterised in that cellulosic solid waste powder：Modifying agent：Auxiliary agent= 100：5-30：1-8, mass ratio.
3. according to any described preparation methods of claim 1-2, it is characterised in that the modifying agent include oxalic acid, malonic acid, Butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, maleic acid, butene dioic acid, glutaconate, malic acid, amino acid, lemon Any of lemon acid, ethylenediamine, diisopropylamine, triethanolamine, diethylenetriamine, urea or two or more combinations.
4. preparation method according to claim 3, it is characterised in that the auxiliary agent is AlCl3、KNO3、Na2CO3、 Li2P2O7、Na4P2O7、ZnCl2、MgCO3Any of or two or more combinations.
5. preparation method according to claim 3, it is characterised in that the molysite is FeCl3、Fe(NO3)3、Fe2(SO4)3 Any of or two or more combinations, the ferrous salt be FeCl2、Fe(NO3)2、FeSO4Any of or two kinds with On combination.
6. preparation method according to claim 5, it is characterised in that molysite and/or ferrous salt solution total mass concentration are 2-10%.
7. according to any described preparation methods of claim 4-6, it is characterised in that mixture and grinding media heap volume according to 100g：200-600mL ratio is added in mechanical activation solid phase reactor, is 200-600rpm and 30-60 DEG C of constant temperature in rotating speed Under the conditions of carry out ball-milling reaction, after reaction 0.5-1.5h, stop heating and stir, separation product and abrading-ball obtain being modified wooden Cellulose ester mixture.
8. according to any described preparation methods of claim 1-2, it is characterised in that cellulosic solid waste dries, crush will Ask for：Water content is less than 15%, is crushed to 20-60 mesh, and modified wood fibre element ester admixture is added under conditions of stirring After in molysite and/or ferrous salt solution, refiltered after standing, time of repose is 0.5-24h.
9. according to any described preparation methods of claim 1-2, it is characterised in that described cellulosic solid waste is sugarcane Slag, cassava grain stillage, Cassava stalk, wood chip, bamboo scraps, stalk, ramulus mori any one or two or more combinations.
10. the plain ester group class fenton catalyst of modified wood fibre that the preparation method as described in claim any one of 1-9 is obtained Application in the treatment of waste water.
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