CN105771911B - A kind of loading β type FeOOH modified natural fibers element functional form materials and preparation method and application - Google Patents
A kind of loading β type FeOOH modified natural fibers element functional form materials and preparation method and application Download PDFInfo
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- CN105771911B CN105771911B CN201610118936.3A CN201610118936A CN105771911B CN 105771911 B CN105771911 B CN 105771911B CN 201610118936 A CN201610118936 A CN 201610118936A CN 105771911 B CN105771911 B CN 105771911B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- B01J2220/00—Aspects relating to sorbent materials
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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Abstract
The present invention relates to a kind of loading β type FeOOH modified natural fibers element functional form materials and preparation method and application, belong to industrial waste water treatment.The preparation method of the material includes three big step of the preparation of native cellulose, the modification of native cellulose and loading β types FeOOH, obtained functional form material has more absorption point positions and a variety of absorption properties, other ions and the salinity in water can be adsorbed, solves the strong brine processing problem that current arsenic-containing waste water advanced treating faces.The functional material adsorption capacity is strong, and treated, and arsenic-containing waste water aqueous concentration is less than 0.05mg/L, can be desorbed according to the making choice property of mode difference of absorption, and degradable, no environmental toxicity, application easy to spread.
Description
Technical field
The invention belongs to industrial waste water treatments, and in particular to a kind of loading β type FeOOH modified naturals
Cellulose functional form material and preparation method and application.
Background technology
Arsenic is a kind of plasm poisonous substance, can pass through the sulfydryl with albumen and enzyme（—SH）Interaction（Make protein and enzyme
It is denatured in the cell）And increase intracellular active oxygen and cause cellular damage and generate toxicity, by U.S.'s disease control
The heart（CDC）And international cancer research institution（IARC）It is determined as first kind carcinogen.Arsenic also has genetoxic, belongs to the world
Health organization（WHO）Priority pollutants.
Arsenic removal technology mainly has the precipitation method, ion-exchange, membrane separation process, bioanalysis and absorption method etc. both at home and abroad at present,
And the precipitation method and absorption method application are most.Pretreatment stage, the precipitation method are most widely used；The advanced treating stage, membrane separation process,
Absorption method is using more.Wherein, absorption method because adsorbent diversity, it can be achieved that efficiently, low cost production and it is extensive
Using.It can be used as the active charcoal of material of adsorbent, chitosan, activated aluminum, flyash, bone carbon, lime, functional resin etc..But
Be these adsorbents greatly most without good cavernous structure, the features such as adsorbance is small, and due to AsO2 -And AsO4 3Generally coexist
In the waste water containing arsenic, the product after absorption has larger bio-toxicity.
Preferable arsenic-removing adsorption agent should be not only efficient, but also cheap, and can remove trivalent arsenic and pentavalent arsenic simultaneously, used
Adsorbent being capable of desorption and regeneration.It has been reported that and makees carrier on spherical gossypin, be developed into the spherical cotton of load iron (β-FeOOH)
Cellulose adsorbent (number of patent application: 200410019876.7).The preparation and application of this novel adsorbent, both at home and abroad
There is not yet research report, the main active of adsorbent is β types FeOOH (β-FeOOH）, but this adsorbent
Adsorption site is less.
The common problem with reference to present in current arsenic-containing waste water processing item, traditional technique are：Raw water → aerating oxidation
→ flocculation sediment → advanced treating → water outlet.In this process section, mainly chemical precipitation, electric flocculation that flocculation sediment uses
Deng introducing Ca although most heavy metal ion and arsenic in water removal can be removed, during this2+, Fe ions, Al3 +、SO42-Plasma, in the advanced treating stage, to reach existing national standard, generally in end using membrane filtration, reverse osmosis
Even depth treatment process, although the arsenic content of water outlet can handle 0.01mg/L, the concentrated water electrical conductivity generated is high, salinity
High, retention arsenic ion is also included within the inside, it is impossible to reach discharge standard.This part concentrated water is big, of high cost with intractability
The features such as.If the functional form sorbing material and technique of a kind of advanced treating for arsenic-containing waste water can be developed, by its reality
It is obtained in actual engineering, realizes qualified discharge, reduce processing cost, this will be containing arsenic and other heavy metal-containing waste waters
Improvement bring new dawn.
The content of the invention
It is an object of the present invention to solve the deficiency of the existing technology and provide a kind of loading β types FeOOHs to be modified day
Right cellulose functional form material and preparation method and application.The present invention uses native cellulose, Ran Houtong made of bagasse
The methods of peroxidating, graft copolymerization, is modified it, reloads β types FeOOH (β-FeOOH）Environmentally friendly function is made
Material, the functional material are used for the processing of arsenic-containing waste water, in adsorbed water body while arsenic ion, since it has more absorption
Point position and a variety of absorption properties, can adsorb other ions and the salinity in water, solve current arsenic-containing waste water advanced treating face
The strong brine processing problem faced.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method for loading β type FeOOH modified natural fibers element functional form materials, includes the following steps：
Step（1）, the preparation of native cellulose：
A. bagasse is added in into the mixed solvent to ethyl alcohol and toluene, is stirred to react 5.5-6.5h at room temperature, filtered,
Filter residue is washed with deionized to remove solvent；The solid-to-liquid ratio of bagasse and ethyl alcohol is 1：10-15；The solid-liquid of bagasse and toluene
Than being 1：4-6；
B. the filter residue after a steps are washed is added to the NaClO of acidifying with acetic acid2In solution, 1.5- is reacted at 74-76 DEG C
2h, filtering, filter residue is washed with deionized to neutrality, spare；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is
1：5.5-6；The NaClO of the acidifying with acetic acid2The preparation method of solution is by NaClO2It is its 24-26 times to be added to quality
In deionized water, then again with glacial acetic acid by pH be transferred to 3 to get；
C. the filter residue obtained through step b processing is soaked in the KOH aqueous solutions that mass concentration is 2%, reacted at room temperature
23-25h, filtering, filter residue is washed with deionized to neutrality, spare；
D. step c is repeated 3-4 times；
E. the filter residue obtained through step d processing is soaked in the KOH aqueous solutions that mass concentration is 6%, it is anti-at 79-81 DEG C
1.9-2.1h is answered, is filtered, filter residue is washed with deionized to neutrality, spare；
F. the filter residue obtained through step e processing is soaked in the hydrochloric acid that mass concentration is 1%, in 79-81 DEG C of reaction
0.9-1h, filtering, filter residue are washed with deionized to neutrality, are dried in vacuo, are obtained Bagasse-cellulose, i.e. natural fiber
Element；
Step（2）, native cellulose connects branch modification by copolymerization：Take step（1）Bagasse-cellulose obtained is added to
In ionized water, after being warming up to 109-111 DEG C under nitrogen atmosphere, it is Bagasse-cellulose 0.002%-0.006% to add in quality
Potassium permanganate carries out pre-oxidation, and adding in acrylic acid after 30-45min carries out graft copolymerization, after reacting 175-185min,
Add in the benzenediol aqueous solution that mass concentration is 1-2%；Cleaning 2-4 times is carried out with the ethyl alcohol that volumetric concentration is 95% again, is filtered, filter
Slag is cleaned with deionized water to neutrality, dry, obtains modified bagasse cellulose；
Wherein, the solid-to-liquid ratio of Bagasse-cellulose and deionized water is 1：19-21；Bagasse-cellulose and acrylic acid are consolidated
Liquor ratio is 1：4-10；The solid-to-liquid ratio of Bagasse-cellulose and benzenediol aqueous solution is 1：2-4；Bagasse-cellulose and cleaning every time
The solid-to-liquid ratio of required ethyl alcohol is 1：9-11；
Step（3）, load β type FeOOHs：By step（2）Modified bagasse cellulose obtained is immersed in 3mol/L
Sodium hydrate aqueous solution in carry out basification, after 0.9-1.1h, it is Bagasse-cellulose to add in quality（It is not to change herein
On the basis of property Bagasse-cellulose, but with step（2）Bagasse-cellulose on the basis of, similarly hereinafter）The iron powder of quality 10-20%,
And it carries out being stirred to react 0.45-0.55h；The sodium hydrate aqueous solution of 2mol/L is added afterwards, after reacting 23-25h, filtering,
Filter residue is taken, is cleaned with deionized water to colourless, is dried at 59-61 DEG C to get loading β type FeOOH modified naturals
Cellulose functional form material；
Wherein, the solid-to-liquid ratio of the sodium hydrate aqueous solution of Bagasse-cellulose and 2mol/L is 1：3-4.
It is further preferred that the preparation of the loading β type FeOOH modified natural fibers element functional form materials
Method includes the following steps：
Step（1）, the preparation of native cellulose：
A. bagasse is added in into the mixed solvent to ethyl alcohol and toluene, is stirred to react 5h at room temperature, filtered, spend from
Sub- water washing filter residue is to remove solvent；The solid-to-liquid ratio of bagasse and ethyl alcohol is 1：12；The solid-to-liquid ratio of bagasse and toluene is 1：5；
B. the filter residue after a steps are washed is added to the NaClO of acidifying with acetic acid2In solution, 1.6h, mistake are reacted at 75 DEG C
Filter, filter residue is washed with deionized to neutrality, spare；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1：5.7；
The NaClO of the acidifying with acetic acid2The preparation method of solution is by NaClO2Being added to quality is in its 25 times deionized water,
Then again with glacial acetic acid by pH be transferred to 3 to get；
C. the filter residue obtained through step b processing is soaked in the KOH aqueous solutions that mass concentration is 2%, reacted at room temperature
For 24 hours, filter, filter residue is washed with deionized to neutrality, spare；
D. step c is repeated 3 times；
E. the filter residue obtained through step d processing is soaked in the KOH aqueous solutions that mass concentration is 6%, in 80 DEG C of reactions
2h, filtering, filter residue is washed with deionized to neutrality, spare；
F. the filter residue obtained through step e processing is soaked in the hydrochloric acid that mass concentration is 1%, reacts 0.95h in 80 DEG C,
Filtering, filter residue are washed with deionized to neutrality, are dried in vacuo, are obtained Bagasse-cellulose, i.e. native cellulose；
Step（2）, native cellulose connects branch modification by copolymerization：Take step（1）Bagasse-cellulose obtained is added to
In ionized water, after 110 DEG C are warming up under nitrogen atmosphere, add in the potassium permanganate that quality is Bagasse-cellulose 0.004% and carry out
Pre-oxidation adds in acrylic acid after 40min and carries out graft copolymerization, and after reacting 180min, it is 1.5% to add in mass concentration
Benzenediol aqueous solution；Cleaning 3 times is carried out with the ethyl alcohol that volumetric concentration is 95% again, is filtered, filter residue is cleaned with deionized water into
Property after, it is dry, obtain modified bagasse cellulose；
Wherein, the solid-to-liquid ratio of Bagasse-cellulose and deionized water is 1：20；The solid-liquid of Bagasse-cellulose and acrylic acid
Than for 1：6；The solid-to-liquid ratio of Bagasse-cellulose and benzenediol aqueous solution is 1：3；Bagasse-cellulose and second needed for cleaning every time
The solid-to-liquid ratio of alcohol is 1：10；
Step（3）, load β type FeOOHs：By step（2）Modified bagasse cellulose obtained is immersed in 3mol/L
Sodium hydrate aqueous solution in carry out basification, after 1h, add in the iron powder that quality is Bagasse-cellulose quality 15%, go forward side by side
Row is stirred to react 0.5h；Add the sodium hydrate aqueous solution of 2mol/L afterwards, after reaction for 24 hours, filtering takes filter residue, spend from
Sub- water is cleaned to colourless, is dried at 60 DEG C to get loading β type FeOOH modified natural fibers element function section bars
Material；
Wherein, the solid-to-liquid ratio of the sodium hydrate aqueous solution of Bagasse-cellulose and 2mol/L is 1：3.5.
A kind of system of above-mentioned loading β types FeOOH modified natural fibers element functional form material is also claimed in the present invention
Preparation Method loading β type FeOOH modified natural fibers element functional form materials obtained.
The present invention requires in addition that a kind of above-mentioned loading β types FeOOH modified natural fibers element functional form material of protection
Application of the preparation method loading β type FeOOH modified natural fibers element functional form materials obtained in water process, preferably
Refer to arsenic-containing waste water processing in application.
The present invention also provides a kind of arsenic-containing waste water processing system, including sequentially connected aeration oxidation pool, flocculation sedimentation tank,
Reactor and clarifying basin, the built-in above-mentioned preparation method loading β types FeOOH obtained that is filled with of the reactor are modified day
Right cellulose functional form material.
It is further preferred that the reactor has multiple, and it is arranged in series.
It is further preferred that the reactor has 2, i.e. first reactor and second reactor；
Aeration oxidation pool water inlet is equipped with intake pump, and the water outlet of aeration oxidation pool passes through the first valve and flocculation sediment
The water inlet in pond is connected, and flocculation sedimentation tank bottom is equipped with mud valve, and the water outlet of flocculation sedimentation tank passes through the second valve and first
The water inlet of reactor bottom is connected, and the water outlet of first reactor bottom passes through the 3rd valve and entering at the top of second reactor
The mouth of a river is connected, and the water outlet of second reactor bottom is connected by the 4th valve with the water inlet of clarifying basin；
The bottom of clarifying basin is equipped with blowdown valve；
The bottom of the aeration oxidation pool is equipped with aeration head, and the aeration head and gas flowmeter, aeration pump are successively
It is connected；Aeration pump is also connected with the power output end of frequency converter, and the power input of frequency converter is electrically connected with PLC；
Multiple dissolved oxygen electrodes are additionally provided in the aeration oxidation pool, these dissolved oxygen electrodes and online dissolved oxygen instrument
Output terminal is connected, and the input terminal of online dissolved oxygen instrument is electrically connected with PLC.
The present invention additionally provides a kind of method for treating arsenic-containing wastewater, are handled using above-mentioned arsenic-containing waste water processing system,
Step is as follows：
Arsenic-containing waste water enters aeration oxidation pool through intake pump and carries out aerating oxidation 20-30min, and during aerating oxidation, control exposes
The dissolved oxygen value DO of arsenic-containing waste water is 2-4mg/L in gas oxidation pond；
It is entered by the arsenic-containing waste water of aerating oxidation and flocculation sediment is carried out in flocculation sedimentation tank；Arsenic in flocculation sediment water inlet
Content≤200mg/L, pH6-9, the residence time in arsenic-containing waste water flocculation sedimentation tank are 45-50min；Contain arsenic through flocculation sediment
Wastewater pH is 6-9, arsenic content≤10mg/L；
Then the arsenic-containing waste water through flocculation sediment is passed through in reactor and reacted, reaction time 28-33min；
Waste water in reacted device after reaction treatment, which enters clarifying basin clarification, to discharge；The wherein effective depth of clarifying basin
H is 1.5-2m, and the residence time HRT of waste water is 11-13h during clarification.
It is further preferred that the flocculant used in the flocculation sedimentation tank is calcium hydroxide, usage amount 0.5-
0.65mg/L。
Compared with prior art, the present invention its advantage is：
（1）The present invention using native cellulose made of bagasse, first aoxidized, graft copolymerization, the side such as esterified, etherificate
Method is modified, and then it is modified by the methods of oxidation, graft copolymerization, reloads β types FeOOH (β-FeOOH）Ring is made
Border friendly functional material, the functional material are used for the processing of arsenic-containing waste water, can not only arsenic ion in adsorbed water body, due also to
It is built bridge, Electrostatic Absorption, ion exchange, object with more hydrogen bonds, hydroxyl radical free radical, the functional group with amino by ion
Reason absorption and some other physics chemical actions, can adsorb other ions and the salinity in water, solve current arsenic-containing waste water
The strong brine processing problem that advanced treating faces.The functional material is also strong with adsorption capacity, maximum adsorption capacity As（With total arsenic
Meter）128mg/g is can reach, treated, and arsenic-containing waste water aqueous concentration is less than 0.05mg/L, degradable, alternative desorption, nothing
The advantages that environmental toxicity.
（2）The process route that arsenic-containing waste water processing system of the present invention uses：Raw water → aerating oxidation → flocculation sediment → anti-
Answer device → water outlet, solve the strong brine processing that conventional process arsenic-containing waste water need to carry out generating after advanced treating and processing it is difficult, into
This high problem, and applied in practice in engineering.
（3）Utilized head pressure of the present invention by horizontal permeation pressure, allows process object arsenic-containing waste water to walk in systems.
This technique can ensure that the pollutant of water and the inside is sufficiently contacted, and when water uplink stage in the reactor, ooze
Thoroughly under the action of pressure, function sorbing material can be made more to adsorb ion and polluter in water.
Description of the drawings
Fig. 1 is the structure diagram of 4 arsenic-containing waste water processing system of the embodiment of the present invention.
Wherein, 1, aeration oxidation pool；2nd, flocculation sedimentation tank；3rd, first reactor；4th, second reactor；5th, clarifying basin；6、
Intake pump；7th, the first valve；8th, mud valve；9th, the second valve；10th, the 3rd valve；11st, the 4th valve；12nd, blowdown valve；13rd, expose
Gas head；14th, gas flowmeter；15th, aeration pump；16th, frequency converter；17、PLC；18th, dissolved oxygen electrode；19th, online dissolved oxygen instrument；
20th, filler.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and it should not be regarded as limiting this hair
Bright scope.In the examples where no specific technique or condition is specified, according to the described technology of document in the art or condition
Or it is carried out according to product description.Reagents or instruments used without specified manufacturer, being can be by buying what is obtained
Conventional products.
Solid-to-liquid ratio of the present invention is the quality of solid and the volume ratio of liquid, and unit is g/ml.
Embodiment 1
A kind of preparation method for loading β type FeOOH modified natural fibers element functional form materials, includes the following steps：
Step（1）, the preparation of native cellulose：
A. bagasse is added in into the mixed solvent to ethyl alcohol and toluene, is stirred to react 5.5h at room temperature, filtered, spend
Ion water washing filter residue is to remove solvent；The solid-to-liquid ratio of bagasse and ethyl alcohol is 1：10；The solid-to-liquid ratio of bagasse and toluene is 1：
4；
B. the filter residue after a steps are washed is added to the NaClO of acidifying with acetic acid2In solution, 1.5h is reacted at 74 DEG C, with
Lignin is removed, filtering, filter residue is washed with deionized to neutrality, spare；The NaClO of bagasse and acidifying with acetic acid2Solution
Solid-to-liquid ratio is 1：5.5；The NaClO of the acidifying with acetic acid2The preparation method of solution is by NaClO2It is its 24 times to be added to quality
Deionized water in, then again with glacial acetic acid by pH be transferred to 3 to get；
C. the filter residue obtained through step b processing is soaked in the KOH aqueous solutions that mass concentration is 2%, reacted at room temperature
23h, to remove hemicellulose, filtering, filter residue is washed with deionized to neutrality, spare；
D. repeat step c 3 times, obtain the powdered rubber of white；
E. the filter residue that will be obtained through step d processing（The powdered rubber of white）It is water-soluble to be soaked in the KOH that mass concentration is 6%
In liquid, 1.9h is reacted at 79 DEG C, thoroughly to remove hemicellulose, filtering, filter residue is washed with deionized to neutrality, spare；
F. the filter residue obtained through step e processing is soaked in the hydrochloric acid that mass concentration is 1%, reacts 0.9h in 79 DEG C and remove
Miscellaneous, filtering, filter residue is washed with deionized to neutrality, is dried in vacuo, is obtained Bagasse-cellulose, i.e. native cellulose；
Step（2）, native cellulose connects branch modification by copolymerization：Take step（1）Bagasse-cellulose obtained is added to
In ionized water, after 109 DEG C are warming up under nitrogen atmosphere, the potassium permanganate that quality is Bagasse-cellulose 0.002% is added in（Draw
Send out agent）Pre-oxidation is carried out, adding in acrylic acid after 30min carries out graft copolymerization, and after reacting 175min, it is dense to add in quality
Spend the benzenediol aqueous solution for 1%（Polymerization inhibitor）；Cleaning 2 times is carried out with the ethyl alcohol that volumetric concentration is 95% again, is filtered, filter residue is spent
Ionized water is cleaned to neutrality, dry, obtains modified bagasse cellulose；
Wherein, the solid-to-liquid ratio of Bagasse-cellulose and deionized water is 1：19；The solid-liquid of Bagasse-cellulose and acrylic acid
Than for 1：4；The solid-to-liquid ratio of Bagasse-cellulose and benzenediol aqueous solution is 1：2；Bagasse-cellulose and second needed for cleaning every time
The solid-to-liquid ratio of alcohol is 1：9；
Step（3）, load β type FeOOHs：By step（2）Modified bagasse cellulose obtained is immersed in 3mol/L
Sodium hydrate aqueous solution in carry out basification, after 0.9h, add in the iron powder that quality is Bagasse-cellulose quality 10%, and
It is stirred reaction 0.45h；The sodium hydrate aqueous solution of 2mol/L is added afterwards, and after reacting 23h, filtering takes filter residue, spends
Ionized water is cleaned to colourless, is dried at 59 DEG C to get loading β type FeOOH modified natural fibers element function section bars
Material；
Wherein, the solid-to-liquid ratio of the sodium hydrate aqueous solution of Bagasse-cellulose and 2mol/L is 1：3.
Embodiment 2
A kind of preparation method for loading β type FeOOH modified natural fibers element functional form materials, includes the following steps：
Step（1）, the preparation of native cellulose：
A. bagasse is added in into the mixed solvent to ethyl alcohol and toluene, is stirred to react 5h at room temperature, filtered, spend from
Sub- water washing filter residue is to remove solvent；The solid-to-liquid ratio of bagasse and ethyl alcohol is 1：12；The solid-to-liquid ratio of bagasse and toluene is 1：5；
B. the filter residue after a steps are washed is added to the NaClO of acidifying with acetic acid2In solution, 1.6h is reacted at 75 DEG C, with
Lignin is removed, filtering, filter residue is washed with deionized to neutrality, spare；The NaClO of bagasse and acidifying with acetic acid2Solution
Solid-to-liquid ratio is 1：5.7；The NaClO of the acidifying with acetic acid2The preparation method of solution is by NaClO2It is its 25 times to be added to quality
Deionized water in, then again with glacial acetic acid by pH be transferred to 3 to get；
C. the filter residue obtained through step b processing is soaked in the KOH aqueous solutions that mass concentration is 2%, reacted at room temperature
For 24 hours, to remove hemicellulose, filter, filter residue is washed with deionized to neutrality, spare；
D. repeat step c 3 times, obtain the powdered rubber of white；
E. the filter residue that will be obtained through step d processing（The powdered rubber of white）It is water-soluble to be soaked in the KOH that mass concentration is 6%
In liquid, 2h is reacted at 80 DEG C, thoroughly to remove hemicellulose, filtering, filter residue is washed with deionized to neutrality, spare；
F. the filter residue obtained through step e processing is soaked in the hydrochloric acid that mass concentration is 1%, reacts 0.95h in 80 DEG C
Removal of impurities, filtering, filter residue are washed with deionized to neutrality, are dried in vacuo, are obtained Bagasse-cellulose, i.e. native cellulose；
Step（2）, native cellulose connects branch modification by copolymerization：Take step（1）Bagasse-cellulose obtained is added to
In ionized water, after 110 DEG C are warming up under nitrogen atmosphere, the potassium permanganate that quality is Bagasse-cellulose 0.004% is added in（Draw
Send out agent）Pre-oxidation is carried out, adding in acrylic acid after 40min carries out graft copolymerization, and after reacting 180min, it is dense to add in quality
Spend the benzenediol aqueous solution for 1.5%（Polymerization inhibitor）；Cleaning 3 times is carried out with the ethyl alcohol that volumetric concentration is 95% again, is filtered, filter residue is used
Deionized water is cleaned to neutrality, dry, obtains modified bagasse cellulose；
Wherein, the solid-to-liquid ratio of Bagasse-cellulose and deionized water is 1：20；The solid-liquid of Bagasse-cellulose and acrylic acid
Than for 1：6；The solid-to-liquid ratio of Bagasse-cellulose and benzenediol aqueous solution is 1：3；Bagasse-cellulose and second needed for cleaning every time
The solid-to-liquid ratio of alcohol is 1：10；
Step（3）, load β type FeOOHs：By step（2）Modified bagasse cellulose obtained is immersed in 3mol/L
Sodium hydrate aqueous solution in carry out basification, after 1h, add in the iron powder that quality is Bagasse-cellulose quality 15%, go forward side by side
Row is stirred to react 0.5h；Add the sodium hydrate aqueous solution of 2mol/L afterwards, after reaction for 24 hours, filtering takes filter residue, spend from
Sub- water is cleaned to colourless, is dried at 60 DEG C to get loading β type FeOOH modified natural fibers element function section bars
Material；
Wherein, the solid-to-liquid ratio of the sodium hydrate aqueous solution of Bagasse-cellulose and 2mol/L is 1：3.5.
Embodiment 3
A kind of preparation method for loading β type FeOOH modified natural fibers element functional form materials, includes the following steps：
Step（1）, the preparation of native cellulose：
A. bagasse is added in into the mixed solvent to ethyl alcohol and toluene, is stirred to react 6.5h at room temperature, filtered, spend
Ion water washing filter residue is to remove solvent；The solid-to-liquid ratio of bagasse and ethyl alcohol is 1：15；The solid-to-liquid ratio of bagasse and toluene is 1：
6；
B. the filter residue after a steps are washed is added to the NaClO of acidifying with acetic acid2In solution, 2h is reacted at 76 DEG C, to go
Except lignin, filtering, filter residue is washed with deionized to neutrality, spare；The NaClO of bagasse and acidifying with acetic acid2Solution is consolidated
Liquor ratio is 1：6；The NaClO of the acidifying with acetic acid2The preparation method of solution is by NaClO2Being added to quality is its 26 times
In ionized water, then again with glacial acetic acid by pH be transferred to 3 to get；
C. the filter residue obtained through step b processing is soaked in the KOH aqueous solutions that mass concentration is 2%, reacted at room temperature
25h, to remove hemicellulose, filtering, filter residue is washed with deionized to neutrality, spare；
D. repeat step c 4 times, obtain the powdered rubber of white；
E. the filter residue that will be obtained through step d processing（The powdered rubber of white）It is water-soluble to be soaked in the KOH that mass concentration is 6%
In liquid, 2.1h is reacted at 81 DEG C, thoroughly to remove hemicellulose, filtering, filter residue is washed with deionized to neutrality, spare；
F. the filter residue obtained through step e processing is soaked in the hydrochloric acid that mass concentration is 1%, reacts 1h in 81 DEG C and remove
Miscellaneous, filtering, filter residue is washed with deionized to neutrality, is dried in vacuo, is obtained Bagasse-cellulose, i.e. native cellulose；
Step（2）, native cellulose connects branch modification by copolymerization：Take step（1）Bagasse-cellulose obtained is added to
In ionized water, after 111 DEG C are warming up under nitrogen atmosphere, the potassium permanganate that quality is Bagasse-cellulose 0.006% is added in（Draw
Send out agent）Pre-oxidation is carried out, adding in acrylic acid after 45min carries out graft copolymerization, after reacting 185min, adds in quality
Concentration is 12% benzenediol aqueous solution（Polymerization inhibitor）；Cleaning 4 times is carried out with the ethyl alcohol that volumetric concentration is 95% again, is filtered, filter residue
It is cleaned with deionized water to neutrality, it is dry, obtain modified bagasse cellulose；
Wherein, the solid-to-liquid ratio of Bagasse-cellulose and deionized water is 1：21；The solid-liquid of Bagasse-cellulose and acrylic acid
Than for 1：10；The solid-to-liquid ratio of Bagasse-cellulose and benzenediol aqueous solution is 1：4；Bagasse-cellulose and second needed for cleaning every time
The solid-to-liquid ratio of alcohol is 1：11；
Step（3）, load β type FeOOHs：By step（2）Modified bagasse cellulose obtained is immersed in 3mol/L
Sodium hydrate aqueous solution in carry out basification, after 1.1h, add in the iron powder that quality is Bagasse-cellulose quality 20%, and
It is stirred reaction 0.55h；The sodium hydrate aqueous solution of 2mol/L is added afterwards, and after reacting 25h, filtering takes filter residue, spends
Ionized water is cleaned to colourless, is dried at 61 DEG C to get loading β type FeOOH modified natural fibers element function section bars
Material；
Wherein, the solid-to-liquid ratio of the sodium hydrate aqueous solution of Bagasse-cellulose and 2mol/L is 1：4.
Embodiment 4
As shown in Figure 1, a kind of arsenic-containing waste water processing system, including sequentially connected aeration oxidation pool 1, flocculation sedimentation tank 2,
Reactor and clarifying basin 5, the reactor is built-in to be filled with the loading β type FeOOHs modified natural fibre obtained of embodiment 2
The plain functional form material of dimension, forms filler 20.
The reactor can be 1, it is possibility to have it is multiple, when for it is multiple when only need to be arranged in series.This reality
Applying example has 2 reactors, is first reactor 3 and second reactor 4.
1 water inlet of aeration oxidation pool is equipped with intake pump 6, and the water outlet of aeration oxidation pool 1 passes through the first valve 7 and flocculation
The water inlet of sedimentation basin 2 is connected, and 2 bottom of flocculation sedimentation tank is equipped with mud valve 8, and the water outlet of flocculation sedimentation tank 2 passes through the second valve
Door 9 is connected with the water inlet of 3 bottom of first reactor, and the water outlet of 3 bottom of first reactor passes through the 3rd valve 10 and second
The water inlet at the top of reactor 4 is connected, and the water outlet of 4 bottom of second reactor enters water by the 4th valve 11 and clarifying basin 5
Mouth is connected；
The bottom of clarifying basin 5 is equipped with blowdown valve 12；
The bottom of the aeration oxidation pool 1 is equipped with aeration head 13, the aeration head 13 and gas flowmeter 14, aeration
Pump 15 is sequentially connected；Power output end of the aeration pump 15 also with frequency converter 16 is connected, the power input of frequency converter 16 with
PLC17 is electrically connected；
Multiple dissolved oxygen electrodes 18 are additionally provided in the aeration oxidation pool 1, these dissolved oxygen electrodes 18 and online dissolving
The output terminal of oxygen instrument 19 is connected, and the input terminal of online dissolved oxygen instrument 19 is electrically connected with PLC17.The present embodiment has 2 dissolved oxygen electricity
Pole 18.
Embodiment 5
A kind of method for treating arsenic-containing wastewater, selects Yunnan mountain of papers arsenic factory arsenic-containing waste water, and influent concentration arsenic content is
128mg/L, pH 4.5 is handled using the arsenic-containing waste water processing system of embodiment 4, and step is as follows：
Arsenic-containing waste water enters aeration oxidation pool through intake pump and carries out aerating oxidation 25min, during aerating oxidation, control aeration oxygen
The dissolved oxygen value DO for changing arsenic-containing waste water in pond is 2.6mg/L；
It is entered by the arsenic-containing waste water of aerating oxidation and flocculation sediment is carried out in flocculation sedimentation tank；Arsenic in flocculation sediment water inlet
Content≤200mg/L, pH6-9, the residence time in arsenic-containing waste water flocculation sedimentation tank are 48min；It gives up through flocculation sediment containing arsenic
Water pH be 6-9, arsenic content≤10mg/L；
Then the arsenic-containing waste water through flocculation sediment is passed through in reactor and reacted, reaction time 30min；
Waste water in reacted device after reaction treatment, which enters clarifying basin clarification, to discharge；The wherein effective depth of clarifying basin
H is 1.8m, and the residence time HRT of waste water is 12h during clarification.
The flocculant used in the flocculation sedimentation tank is calcium hydroxide, usage amount 0.58mg/L.
Go out water monitoring arsenic concentration for 0.018mg/L, reach existing discharge standard.
Embodiment 6
A kind of method for treating arsenic-containing wastewater selects Yunnan chemical plant arsenic-containing waste water, and influent concentration arsenic content is 85mg/L,
PH is 5, is handled using the arsenic-containing waste water processing system of embodiment 4, step is as follows：
Arsenic-containing waste water enters aeration oxidation pool through intake pump and carries out aerating oxidation 20min, during aerating oxidation, control aeration oxygen
The dissolved oxygen value DO for changing arsenic-containing waste water in pond is 2mg/L；
It is entered by the arsenic-containing waste water of aerating oxidation and flocculation sediment is carried out in flocculation sedimentation tank；Arsenic in flocculation sediment water inlet
Content≤200mg/L, pH6-9, the residence time in arsenic-containing waste water flocculation sedimentation tank are 45min；It gives up through flocculation sediment containing arsenic
Water pH be 6-9, arsenic content≤10mg/L；
Then the arsenic-containing waste water through flocculation sediment is passed through in reactor and reacted, reaction time 28min；
Waste water in reacted device after reaction treatment, which enters clarifying basin clarification, to discharge；The wherein effective depth of clarifying basin
H is 1.5m, and the residence time HRT of waste water is 11h during clarification.
The flocculant used in the flocculation sedimentation tank is calcium hydroxide, usage amount 0.5mg/L.
Go out water monitoring arsenic concentration for 0.019mg/L, reach existing discharge standard.
Embodiment 7
A kind of method for treating arsenic-containing wastewater, selects Yunnan Metallurgical Factory arsenic-containing waste water, and influent concentration arsenic content is 135mg/
L, pH 4 is handled using the arsenic-containing waste water processing system of embodiment 4, and step is as follows：
Arsenic-containing waste water enters aeration oxidation pool through intake pump and carries out aerating oxidation 30min, during aerating oxidation, control aeration oxygen
The dissolved oxygen value DO for changing arsenic-containing waste water in pond is 4mg/L；
It is entered by the arsenic-containing waste water of aerating oxidation and flocculation sediment is carried out in flocculation sedimentation tank；Arsenic in flocculation sediment water inlet
Content≤200mg/L, pH6-9, the residence time in arsenic-containing waste water flocculation sedimentation tank are 50min；It gives up through flocculation sediment containing arsenic
Water pH be 6-9, arsenic content≤10mg/L；
Then the arsenic-containing waste water through flocculation sediment is passed through in reactor and reacted, reaction time 33min；
Waste water in reacted device after reaction treatment, which enters clarifying basin clarification, to discharge；The wherein effective depth of clarifying basin
H is 2m, and the residence time HRT of waste water is 13h during clarification.
The flocculant used in the flocculation sedimentation tank is calcium hydroxide, usage amount 0.65mg/L.
Go out water monitoring arsenic concentration for 0.02mg/L, reach existing discharge standard.
Basic principle, main feature and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of preparation method for loading β type FeOOH modified natural fibers element functional form materials, which is characterized in that including
Following steps：
Step（1）, the preparation of native cellulose：
A. bagasse is added in into the mixed solvent to ethyl alcohol and toluene, is stirred to react 5.5-6.5h at room temperature, filtered, spend
Ion water washing filter residue is to remove solvent；The solid-to-liquid ratio of bagasse and ethyl alcohol is 1：10-15；The solid-to-liquid ratio of bagasse and toluene is
1：4-6；
B. the filter residue after a steps are washed is added to the NaClO of acidifying with acetic acid2In solution, 1.5-2h, mistake are reacted at 74-76 DEG C
Filter, filter residue is washed with deionized to neutrality, spare；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1：5.5-
6；The NaClO of the acidifying with acetic acid2The preparation method of solution is by NaClO2It is its 24-26 times deionization to be added to quality
In water, then again with glacial acetic acid by pH be transferred to 3 to get；
C. the filter residue obtained through step b processing is soaked in the KOH aqueous solutions that mass concentration is 2%, reacts 23- at room temperature
25h, filtering, filter residue is washed with deionized to neutrality, spare；
D. step c is repeated 3-4 times；
E. the filter residue obtained through step d processing is soaked in the KOH aqueous solutions that mass concentration is 6%, in 79-81 DEG C of reaction
1.9-2.1h, filtering, filter residue is washed with deionized to neutrality, spare；
F. the filter residue obtained through step e processing is soaked in the hydrochloric acid that mass concentration is 1%, reacts 0.9-1h in 79-81 DEG C,
Filtering, filter residue are washed with deionized to neutrality, are dried in vacuo, are obtained Bagasse-cellulose, i.e. native cellulose；
Step（2）, native cellulose connects branch modification by copolymerization：Take step（1）Bagasse-cellulose obtained is added to deionization
In water, after being warming up to 109-111 DEG C under nitrogen atmosphere, the Gao Meng that quality is Bagasse-cellulose 0.002%-0.006% is added in
Sour potassium carries out pre-oxidation, and adding in acrylic acid after 30-45min carries out graft copolymerization, after reacting 175-185min, adds in
Mass concentration is the benzenediol aqueous solution of 1-2%；Cleaning 2-4 times is carried out with the ethyl alcohol that volumetric concentration is 95% again, is filtered, filter residue is used
Deionized water is cleaned to neutrality, dry, obtains modified bagasse cellulose；
Wherein, the solid-to-liquid ratio of Bagasse-cellulose and deionized water is 1：19-21；The solid-to-liquid ratio of Bagasse-cellulose and acrylic acid
For 1：4-10；The solid-to-liquid ratio of Bagasse-cellulose and benzenediol aqueous solution is 1：2-4；Needed for Bagasse-cellulose and every time cleaning
The solid-to-liquid ratio of ethyl alcohol is 1：9-11；
Step（3）, load β type FeOOHs：By step（2）Modified bagasse cellulose obtained is immersed in the hydrogen of 3mol/L
It carries out basification in aqueous solution of sodium oxide, after 0.9-1.1h, adds in the iron powder that quality is Bagasse-cellulose quality 10-20%,
And it carries out being stirred to react 0.45-0.55h；The sodium hydrate aqueous solution of 2mol/L is added afterwards, after reacting 23-25h, filtering,
Filter residue is taken, is cleaned with deionized water to colourless, is dried at 59-61 DEG C to get loading β type FeOOH modified naturals
Cellulose functional form material；
Wherein, the solid-to-liquid ratio of the sodium hydrate aqueous solution of Bagasse-cellulose and 2mol/L is 1：3-4；
Wherein, the solid-to-liquid ratio is the quality of solid and the volume ratio of liquid, and unit is g/ml.
2. the preparation method of loading β type FeOOH modified natural fibers element functional form materials according to claim 1,
It is characterised in that it includes following steps：
Step（1）, the preparation of native cellulose：
A. bagasse is added in into the mixed solvent to ethyl alcohol and toluene, is stirred to react 5h at room temperature, filtered, use deionized water
Filter residue is washed to remove solvent；The solid-to-liquid ratio of bagasse and ethyl alcohol is 1：12；The solid-to-liquid ratio of bagasse and toluene is 1：5；
B. the filter residue after a steps are washed is added to the NaClO of acidifying with acetic acid2In solution, 1.6h is reacted at 75 DEG C, is filtered, filter
Slag is washed with deionized to neutrality, spare；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1：5.7；It is described
Acidifying with acetic acid NaClO2The preparation method of solution is by NaClO2In its 25 times deionized water, then it is to be added to quality
Again with glacial acetic acid by pH be transferred to 3 to get；
C. the filter residue obtained through step b processing is soaked in the KOH aqueous solutions that mass concentration is 2%, reacted at room temperature for 24 hours,
Filtering, filter residue is washed with deionized to neutrality, spare；
D. step c is repeated 3 times；
E. the filter residue obtained through step d processing is soaked in the KOH aqueous solutions that mass concentration is 6%, reacts 2h, mistake at 80 DEG C
Filter, filter residue is washed with deionized to neutrality, spare；
F. the filter residue obtained through step e processing is soaked in the hydrochloric acid that mass concentration is 1%, reacts 0.95h, mistake in 80 DEG C
Filter, filter residue are washed with deionized to neutrality, are dried in vacuo, are obtained Bagasse-cellulose, i.e. native cellulose；
Step（2）, native cellulose connects branch modification by copolymerization：Take step（1）Bagasse-cellulose obtained is added to deionization
In water, after 110 DEG C are warming up under nitrogen atmosphere, add in the potassium permanganate that quality is Bagasse-cellulose 0.004% and carry out pre- oxygen
Change reaction, adding in acrylic acid after 40min carries out graft copolymerization, after reacting 180min, adds in the benzene that mass concentration is 1.5%
Diphenol aqueous solution；Cleaning 3 times is carried out with the ethyl alcohol that volumetric concentration is 95% again, is filtered, filter residue is cleaned with deionized water to neutrality
Afterwards, it is dry, obtain modified bagasse cellulose；
Wherein, the solid-to-liquid ratio of Bagasse-cellulose and deionized water is 1：20；The solid-to-liquid ratio of Bagasse-cellulose and acrylic acid is
1：6；The solid-to-liquid ratio of Bagasse-cellulose and benzenediol aqueous solution is 1：3；Bagasse-cellulose and ethyl alcohol needed for cleaning every time
Solid-to-liquid ratio is 1：10；
Step（3）, load β type FeOOHs：By step（2）Modified bagasse cellulose obtained is immersed in the hydrogen of 3mol/L
Carry out basification in aqueous solution of sodium oxide, after 1h, adding in quality is the iron powder of Bagasse-cellulose quality 15%, and is stirred
Mix reaction 0.5h；The sodium hydrate aqueous solution of 2mol/L is added afterwards, and after reaction for 24 hours, filtering takes filter residue, uses deionized water
It is cleaned to colourless, is dried at 60 DEG C to get loading β type FeOOH modified natural fibers element functional form materials；
Wherein, the solid-to-liquid ratio of the sodium hydrate aqueous solution of Bagasse-cellulose and 2mol/L is 1：3.5.
3. the preparation method system of the loading β type FeOOH modified natural fibers element functional form materials described in claim 1 or 2
The loading β type FeOOH modified natural fibers element functional form materials obtained.
4. the preparation method system of the loading β type FeOOH modified natural fibers element functional form materials described in claim 1 or 2
Application of the loading β type FeOOH modified natural fibers element functional form materials obtained in water process.
5. the preparation method system of the loading β type FeOOH modified natural fibers element functional form materials described in claim 1 or 2
Application of the loading β types FeOOH modified natural fibers element functional form material obtained in arsenic-containing waste water processing.
6. a kind of arsenic-containing waste water processing system, it is characterised in that：Including sequentially connected aeration oxidation pool, flocculation sedimentation tank, anti-
Device and clarifying basin are answered, the reactor is built-in to be filled with claim 1 loading β type FeOOH modified natural fibers obtained
Plain functional form material.
7. arsenic-containing waste water processing system according to claim 6, it is characterised in that：The reactor have it is multiple, and
It is arranged in series.
8. arsenic-containing waste water processing system according to claim 6, it is characterised in that：The reactor has 2, i.e., first
Reactor and second reactor；
Aeration oxidation pool water inlet is equipped with intake pump, and the water outlet of aeration oxidation pool passes through the first valve and flocculation sedimentation tank
Water inlet is connected, and flocculation sedimentation tank bottom is equipped with mud valve, and the water outlet of flocculation sedimentation tank is reacted by the second valve and first
The water inlet of device bottom is connected, and the water outlet of first reactor bottom passes through the water inlet at the top of the 3rd valve and second reactor
It is connected, the water outlet of second reactor bottom is connected by the 4th valve with the water inlet of clarifying basin；
The bottom of clarifying basin is equipped with blowdown valve；
The bottom of the aeration oxidation pool is equipped with aeration head, and the aeration head is sequentially connected with gas flowmeter, aeration pump；
Aeration pump is also connected with the power output end of frequency converter, and the power input of frequency converter is electrically connected with PLC；
Multiple dissolved oxygen electrodes are additionally provided in the aeration oxidation pool, the output of these dissolved oxygen electrodes and online dissolved oxygen instrument
End is connected, and the input terminal of online dissolved oxygen instrument is electrically connected with PLC.
9. a kind of method for treating arsenic-containing wastewater, the arsenic-containing waste water processing system described in usage right requirement 6-8 any one carries out
Processing, which is characterized in that step is as follows：
Arsenic-containing waste water enters aeration oxidation pool through intake pump and carries out aerating oxidation 20-30min, during aerating oxidation, control aeration oxygen
The dissolved oxygen value DO for changing arsenic-containing waste water in pond is 2-4mg/L；
It is entered by the arsenic-containing waste water of aerating oxidation and flocculation sediment is carried out in flocculation sedimentation tank；Arsenic content in flocculation sediment water inlet
≤ 200mg/L, pH6-9, residence time of the arsenic-containing waste water in flocculation sedimentation tank are 45-50min；It gives up through flocculation sediment containing arsenic
Water pH be 6-9, arsenic content≤10mg/L；
Then the arsenic-containing waste water through flocculation sediment is passed through in reactor and reacted, reaction time 28-33min；
Waste water in reacted device after reaction treatment, which enters clarifying basin clarification, to discharge；The effective depth h of wherein clarifying basin is
1.5-2m, the residence time HRT of waste water is 11-13h during clarification.
10. method for treating arsenic-containing wastewater according to claim 9, which is characterized in that used in the flocculation sedimentation tank
Flocculant be calcium hydroxide, usage amount 0.5-0.65mg/L.
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