CN105771911A - Beta-type-hydroxyl-ferric-oxide-loaded natural-cellulose-modified functional material and preparing method and application thereof - Google Patents
Beta-type-hydroxyl-ferric-oxide-loaded natural-cellulose-modified functional material and preparing method and application thereof Download PDFInfo
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Abstract
The invention relates to a beta-type-hydroxyl-ferric-oxide-loaded natural-cellulose-modified functional material and a preparing method and application thereof, and belongs to the technical field of industrial wastewater treatment.The preparing method of the material includes the steps of preparing natural cellulose, modifying the natural cellulose and loading beta-type hydroxyl ferric oxide.The prepared functional material has more adsorption point locations and multiple adsorption performances, other ions and salt in water can be adsorbed, and the problem of strong brine treatment generated during deep treatment of arsenious wastewater at present is solved.The functional material is high in adsorption capability, the concentration of discharged treated arsenious wastewater is lower than 0.05 mg/L, selective desorption can be carried out according to different adsorption modes, and the function material is easy to degrade, free of environmental toxicity and easy to apply and popularize.
Description
Technical field
The invention belongs to industrial waste water treatment, be specifically related to a kind of loading β type FeOOH modified natural fibers element functional type material and preparation method thereof and application.
Background technology
Arsenic is a kind of protoplasm poisonous substance, cell injury can be caused to produce toxicity by interacting (making protein and enzyme at endoglobular degeneration) with the sulfydryl of albumen and enzyme (SH) and increase intracellular active oxygen, be defined as first kind carcinogen by the Center for Disease Control (CDC) and international cancer research institution (IARC).Arsenic also has genetoxic, belongs to the World Health Organization's priority pollutants.
Arsenic removal technology mainly has the sedimentation method, ion exchange, membrane separation process, bioanalysis and absorption method etc. both at home and abroad at present, and the sedimentation method and absorption method application are at most.Pretreatment stage, the sedimentation method are most widely used；In the advanced treating stage, the application of membrane separation process, absorption method is more.Wherein, absorption method is because the multiformity of adsorbent, it may be achieved efficiently, the production of low cost and be widely used.Can be used as the material of adsorbent and have activated carbon, chitosan, activated aluminum, flyash, bone carbon, Calx, functional resin etc..Features such as but these adsorbents scarcely have good cavernous structure, and adsorbance is little, and due to AsO2 -And AsO4 3Generally coexisting in the waste water containing arsenic, the product after absorption has bigger bio-toxicity.
Desirable arsenic-removing adsorption agent should be both efficient, again inexpensively, and can remove trivalent arsenic and pentavalent arsenic simultaneously, and adsorbent used can desorption and regeneration.Have been reported that and make carrier about spherical gossypin, be developed into load ferrum (β-FeOOH) spherical gossypin adsorbent (number of patent application: 200410019876.7).The preparation of the adsorbent of this novelty and application, there is not yet research report both at home and abroad, and the main active of adsorbent is β type FeOOH (β-FeOOH), but the adsorption site of this adsorbent is less.
In conjunction with common problem in current arsenic-containing waste water processing item, traditional technique is: former water → aerating oxidation → flocculation sediment → advanced treating → water outlet.In this process section, the mainly chemical precipitation that flocculation sediment adopts, electric flocculation etc., although most heavy metal ion and arsenic in water can be removed, but introduce Ca in this process2+, Fe ion, Al3 +、SO42-Plasma, in the advanced treating stage, for reaching existing national standard, being typically in end adopts membrane filtration, reverse osmosis even depth to process technique, although the arsenic content of water outlet can process 0.01mg/L, but the arsenic ion that the dense water conductivity produced is high, salinity is high, retain is also included within the inside, it is impossible to reach discharge standard.The dense glassware for drinking water of this part has that intractability is big, high in cost of production feature.If functional type adsorbing material and the technique of a kind of advanced treating for arsenic-containing waste water can be developed, by in the engineering obtaining reality in its practical application, realizing qualified discharge, reduce processing cost, this is by for bringing new dawn containing the improvement of arsenic and other heavy metal-containing waste waters.
Summary of the invention
The invention aims to solve the deficiencies in the prior art, it is provided that a kind of loading β type FeOOH modified natural fibers element functional type material and preparation method thereof and application.The present invention adopts the native cellulose that bagasse is made, it is modifiied by the methods such as oxidation, graft copolymerization that then pass through, reload β type FeOOH (β-FeOOH) and make environmentally friendly functional material, this functional material is for the process of arsenic-containing waste water, in adsorbed water body while arsenic ion, owing to it has more adsorption site position and multiple absorption property, it is possible to adsorb other ions in water and salinity, solve the strong brine process difficult problem that current arsenic-containing waste water advanced treating faces.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of preparation method loading β type FeOOH modified natural fibers element functional type material, comprises the steps:
Step (1), the preparation of native cellulose:
A. bagasse is added to the mixed solvent of ethanol and toluene, stirring reaction 5.5-6.5h under room temperature, filter, with deionized water wash filtering residue to remove solvent；The solid-to-liquid ratio of bagasse and ethanol is 1:10-15；The solid-to-liquid ratio of bagasse and toluene is 1:4-6；
B. the filtering residue after a step being washed joins the NaClO of acidifying with acetic acid2In solution, reacting 1.5-2h, filter at 74-76 DEG C, filtering residue is extremely neutral with deionized water wash, standby；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1:5.5-6；The NaClO of described acidifying with acetic acid2The preparation method of solution is by NaClO2Joining quality is in its deionized water of 24-26 times, then with glacial acetic acid, pH is transferred to 3 again, to obtain final product；
C. being soaked in by the filtering residue obtained through step b process in the KOH aqueous solution that mass concentration is 2%, at room temperature react 23-25h, filter, filtering residue is extremely neutral with deionized water wash, standby；
D. step c 3-4 time is repeated；
E. being soaked in by the filtering residue obtained through step d process in the KOH aqueous solution that mass concentration is 6%, react 1.9-2.1h at 79-81 DEG C, filter, filtering residue is extremely neutral with deionized water wash, standby；
F. the filtering residue obtained through step e process is soaked in the hydrochloric acid that mass concentration is 1%, in 79-81 DEG C react 0.9-1h, filter, filtering residue deionized water wash to neutrality, vacuum drying, obtain Bagasse-cellulose, i.e. native cellulose；
Step (2), a modification by copolymerization is propped up in connecing of native cellulose: the Bagasse-cellulose taking step (1) prepared joins in deionized water, after being warmed up to 109-111 DEG C under nitrogen atmosphere, add the potassium permanganate that quality is Bagasse-cellulose 0.002%-0.006% and carry out pre-oxidation, add acrylic acid after 30-45min and carry out graft copolymerization, after reaction 175-185min, add the Benzodiazepines aqueous solution that mass concentration is 1-2%；Being carried out 2-4 time with the ethanol that volumetric concentration is 95%, sucking filtration, filtering residue deionized water cleans to neutrality, dry, obtains using modified bagasse cellulose again；
Wherein, Bagasse-cellulose is 1:19-21 with the solid-to-liquid ratio of deionized water；Bagasse-cellulose and acrylic acid solid-to-liquid ratio are 1:4-10；The solid-to-liquid ratio of Bagasse-cellulose and Benzodiazepines aqueous solution is 1:2-4；Bagasse-cellulose is 1:9-11 with each solid-to-liquid ratio cleaning required ethanol；
Step (3), load β type FeOOH: be immersed in the sodium hydrate aqueous solution of 3mol/L and carry out basification by the using modified bagasse cellulose that step (2) prepares, after 0.9-1.1h, addition quality is Bagasse-cellulose (is not with using modified bagasse cellulose for benchmark herein, but with the Bagasse-cellulose of step (2) for benchmark, the iron powder of quality 10-20% down together), and carry out stirring reaction 0.45-0.55h；Add the sodium hydrate aqueous solution of 2mol/L afterwards, after reaction 23-25h, filter, take filtering residue, be carried out to colourless with deionized water, dry at 59-61 DEG C, β type FeOOH modified natural fibers element functional type material must be loaded；
Wherein, Bagasse-cellulose is 1:3-4 with the solid-to-liquid ratio of the sodium hydrate aqueous solution of 2mol/L.
It is further preferred that the described preparation method loading β type FeOOH modified natural fibers element functional type material, comprise the steps:
Step (1), the preparation of native cellulose:
A. bagasse is added to the mixed solvent of ethanol and toluene, stirring reaction 5h under room temperature, filter, with deionized water wash filtering residue to remove solvent；The solid-to-liquid ratio of bagasse and ethanol is 1:12；The solid-to-liquid ratio of bagasse and toluene is 1:5；
B. the filtering residue after a step being washed joins the NaClO of acidifying with acetic acid2In solution, reacting 1.6h, filter at 75 DEG C, filtering residue is extremely neutral with deionized water wash, standby；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1:5.7；The NaClO of described acidifying with acetic acid2The preparation method of solution is by NaClO2Joining quality is in its deionized water of 25 times, then with glacial acetic acid, pH is transferred to 3 again, to obtain final product；
C. being soaked in by the filtering residue obtained through step b process in the KOH aqueous solution that mass concentration is 2%, at room temperature react 24h, filter, filtering residue is extremely neutral with deionized water wash, standby；
D. step c 3 times are repeated；
E. being soaked in by the filtering residue obtained through step d process in the KOH aqueous solution that mass concentration is 6%, react 2h at 80 DEG C, filter, filtering residue is extremely neutral with deionized water wash, standby；
F. the filtering residue obtained through step e process is soaked in the hydrochloric acid that mass concentration is 1%, in 80 DEG C react 0.95h, filter, filtering residue deionized water wash to neutrality, vacuum drying, obtain Bagasse-cellulose, i.e. native cellulose；
Step (2), a modification by copolymerization is propped up in connecing of native cellulose: the Bagasse-cellulose taking step (1) prepared joins in deionized water, after being warmed up to 110 DEG C under nitrogen atmosphere, add the potassium permanganate that quality is Bagasse-cellulose 0.004% and carry out pre-oxidation, add acrylic acid after 40min and carry out graft copolymerization, after reaction 180min, add the Benzodiazepines aqueous solution that mass concentration is 1.5%；Being carried out 3 times with the ethanol that volumetric concentration is 95%, sucking filtration, filtering residue deionized water cleans to neutrality, dry, obtains using modified bagasse cellulose again；
Wherein, Bagasse-cellulose is 1:20 with the solid-to-liquid ratio of deionized water；Bagasse-cellulose and acrylic acid solid-to-liquid ratio are 1:6；The solid-to-liquid ratio of Bagasse-cellulose and Benzodiazepines aqueous solution is 1:3；Bagasse-cellulose is 1:10 with each solid-to-liquid ratio cleaning required ethanol；
Step (3), load β type FeOOH: be immersed in the sodium hydrate aqueous solution of 3mol/L and carry out basification by the using modified bagasse cellulose that step (2) prepares, after 1h, add the iron powder that quality is Bagasse-cellulose quality 15%, and carry out stirring reaction 0.5h；Add the sodium hydrate aqueous solution of 2mol/L afterwards, after reaction 24h, filter, take filtering residue, be carried out to colourless with deionized water, dry at 60 DEG C, β type FeOOH modified natural fibers element functional type material must be loaded；
Wherein, Bagasse-cellulose is 1:3.5 with the solid-to-liquid ratio of the sodium hydrate aqueous solution of 2mol/L.
The present invention is also claimed the loading β type FeOOH modified natural fibers element functional type material that the preparation method of a kind of above-mentioned loading β type FeOOH modified natural fibers element functional type material prepares.
The present invention requires in addition that the loading β type FeOOH modified natural fibers element functional type material protecting the preparation method of a kind of above-mentioned loading β type FeOOH modified natural fibers element functional type material to prepare application in water processes, it is preferred that refer to the application in arsenic-containing waste water processes.
The present invention also provides for a kind of arsenic-containing waste water and processes system, including the aeration oxidation pool being sequentially connected with, flocculation sedimentation tank, reactor and depositing reservoir, described reactor is built-in is filled with the loading β type FeOOH modified natural fibers element functional type material that above-mentioned preparation method prepares.
It is further preferred that described reactor has multiple, and it is arranged in series.
It is further preferred that described reactor has 2, i.e. the first reactor and the second reactor；
Aeration oxidation pool water inlet is provided with intake pump, the outlet of aeration oxidation pool is connected with the water inlet of flocculation sedimentation tank by the first valve, mud valve it is provided with bottom flocculation sedimentation tank, the outlet of flocculation sedimentation tank is connected by the water inlet of the second valve and the first reactor bottom, the outlet of the first reactor bottom is connected by the water inlet of the 3rd valve and the second reactor head, and the outlet of the second reactor bottom is connected with the water inlet of depositing reservoir by the 4th valve；
The bottom of depositing reservoir is provided with blowoff valve；
The bottom of described aeration oxidation pool is provided with aeration head, and described aeration head and gas flowmeter, aeration pump are sequentially connected；Aeration pump is also connected with the power output end of converter, and the power input of converter all electrically connects with PLC；
Being additionally provided with multiple dissolved oxygen electrode in described aeration oxidation pool, these dissolved oxygen electrodes are connected with the outfan of online dissolved oxygen instrument, and the input of online dissolved oxygen instrument electrically connects with PLC.
The present invention additionally provides a kind of method for treating arsenic-containing wastewater, use above-mentioned arsenic-containing waste water to process system and process, 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, controlling the dissolved oxygen value DO of arsenic-containing waste water in aeration oxidation pool is 2-4mg/L；
Arsenic-containing waste water through aerating oxidation enters into and carries out flocculation sediment in flocculation sedimentation tank；Arsenic content≤200mg/L, pH6-9 in flocculation sediment water inlet, the time of staying in arsenic-containing waste water flocculation sedimentation tank is 45-50min；It is 6-9 through the arsenic-containing waste water pH of flocculation sediment, arsenic content≤10mg/L；
Then being passed into by the arsenic-containing waste water through flocculation sediment in reactor and react, the response time is 28-33min；
In reacted device, the waste water entrance depositing reservoir clarification after reaction treatment can be discharged；Wherein the effective depth h of depositing reservoir is 1.5-2m, and during clarification, the time of staying HRT of waste water is 11-13h.
It is further preferred that the flocculant adopted in described flocculation sedimentation tank is calcium hydroxide, making consumption is 0.5-0.65mg/L.
Compared with prior art, it has the beneficial effect that the present invention
(1) present invention adopts the native cellulose that bagasse is made, first aoxidize, graft copolymerization, esterified, the methods such as etherificate modifiy, then pass through oxidation, it is modifiied by the methods such as graft copolymerization, reload β type FeOOH (β-FeOOH) and make environmentally friendly functional material, this functional material is for the process of arsenic-containing waste water, can not only arsenic ion in adsorbed water body, due also to it has more hydrogen bond, hydroxyl radical free radical, functional group with amino, built bridge by ion, Electrostatic Absorption, ion exchanges, physical absorption and some other physics chemical action, other ions in water and salinity can be adsorbed, solve the strong brine process difficult problem that current arsenic-containing waste water advanced treating faces.This functional material also has high adsorption capacity, and maximum adsorption capacity As(is in total arsenic) 128mg/g can be reached, the arsenic-containing waste water aqueous concentration after process is lower than 0.05mg/L, degradable, alternative desorption, without advantages such as environmental toxicities.
(2) arsenic-containing waste water of the present invention processes the process route that system adopts: former water → aerating oxidation → flocculation sediment → reactor → water outlet, solve conventional process arsenic-containing waste water and need to carry out advanced treating, and the strong brine produced after processing processes the difficult problem difficult, cost is high, and obtain application in engineering reality.
(3) utilized head pressure of the present invention, by horizontal permeation pressure, allows process object arsenic-containing waste water walk in systems.This technique ensure that the pollutant of water and the inside contact fully, and when the water up stage in the reactor, under the effect of osmotic pressure, function adsorbing material can be made more to adsorb the ion in water and polluter.
Accompanying drawing explanation
Fig. 1 is the structural representation that the embodiment of the present invention 4 arsenic-containing waste water processes system.
Wherein, 1, aeration oxidation pool；2, flocculation sedimentation tank；3, the first reactor；4, the second reactor；5, depositing reservoir；6, intake pump；7, the first valve；8, mud valve；9, the second valve；10, the 3rd valve；11, the 4th valve；12, blowoff valve；13, aeration head；14, gas flowmeter；15, aeration pump；16, converter；17、PLC；18, dissolved oxygen electrode；19, online dissolved oxygen instrument；20, filler.
Detailed description of the invention
Below in conjunction with 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 should not be taken as limiting the scope of the invention.Unreceipted concrete technology or condition person in embodiment, technology or condition described by the document in this area or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, be and can pass through to buy the conventional products obtained.
Solid-to-liquid ratio of the present invention is the quality volume ratio with liquid of solid, and unit is g/ml.
Embodiment 1
A kind of preparation method loading β type FeOOH modified natural fibers element functional type material, comprises the steps:
Step (1), the preparation of native cellulose:
A. bagasse is added to the mixed solvent of ethanol and toluene, stirring reaction 5.5h under room temperature, filter, with deionized water wash filtering residue to remove solvent；The solid-to-liquid ratio of bagasse and ethanol is 1:10；The solid-to-liquid ratio of bagasse and toluene is 1:4；
B. the filtering residue after a step being washed joins the NaClO of acidifying with acetic acid2In solution, reacting 1.5h at 74 DEG C, to remove lignin, filter, filtering residue is extremely neutral with deionized water wash, standby；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1:5.5；The NaClO of described acidifying with acetic acid2The preparation method of solution is by NaClO2Joining quality is in its deionized water of 24 times, then with glacial acetic acid, pH is transferred to 3 again, to obtain final product；
C. being soaked in by the filtering residue obtained through step b process in the KOH aqueous solution that mass concentration is 2%, at room temperature react 23h, to remove hemicellulose, filter, filtering residue is extremely neutral with deionized water wash, standby；
D. repeat step c 3 times, obtain the powdered rubber of white；
E. being soaked in the KOH aqueous solution that mass concentration is 6% by the filtering residue (powdered rubber of white) obtained through step d process, react 1.9h at 79 DEG C, thoroughly to remove hemicellulose, filter, filtering residue is extremely neutral with deionized water wash, standby；
F. the filtering residue obtained through step e process is soaked in the hydrochloric acid that mass concentration is 1%, in 79 DEG C react 0.9h remove impurity, filter, filtering residue deionized water wash to neutrality, vacuum drying, obtain Bagasse-cellulose, i.e. native cellulose；
Step (2), a modification by copolymerization is propped up in connecing of native cellulose: the Bagasse-cellulose taking step (1) prepared joins in deionized water, after being warmed up to 109 DEG C under nitrogen atmosphere, add the potassium permanganate (initiator) that quality is Bagasse-cellulose 0.002% and carry out pre-oxidation, add acrylic acid after 30min and carry out graft copolymerization, after reaction 175min, add the Benzodiazepines aqueous solution (polymerization inhibitor) that mass concentration is 1%；Being carried out 2 times with the ethanol that volumetric concentration is 95%, sucking filtration, filtering residue deionized water cleans to neutrality, dry, obtains using modified bagasse cellulose again；
Wherein, Bagasse-cellulose is 1:19 with the solid-to-liquid ratio of deionized water；Bagasse-cellulose and acrylic acid solid-to-liquid ratio are 1:4；The solid-to-liquid ratio of Bagasse-cellulose and Benzodiazepines aqueous solution is 1:2；Bagasse-cellulose is 1:9 with each solid-to-liquid ratio cleaning required ethanol；
Step (3), load β type FeOOH: be immersed in the sodium hydrate aqueous solution of 3mol/L and carry out basification by the using modified bagasse cellulose that step (2) prepares, after 0.9h, add the iron powder that quality is Bagasse-cellulose quality 10%, and carry out stirring reaction 0.45h；Add the sodium hydrate aqueous solution of 2mol/L afterwards, after reaction 23h, filter, take filtering residue, be carried out to colourless with deionized water, dry at 59 DEG C, β type FeOOH modified natural fibers element functional type material must be loaded；
Wherein, Bagasse-cellulose is 1:3 with the solid-to-liquid ratio of the sodium hydrate aqueous solution of 2mol/L.
Embodiment 2
A kind of preparation method loading β type FeOOH modified natural fibers element functional type material, comprises the steps:
Step (1), the preparation of native cellulose:
A. bagasse is added to the mixed solvent of ethanol and toluene, stirring reaction 5h under room temperature, filter, with deionized water wash filtering residue to remove solvent；The solid-to-liquid ratio of bagasse and ethanol is 1:12；The solid-to-liquid ratio of bagasse and toluene is 1:5；
B. the filtering residue after a step being washed joins the NaClO of acidifying with acetic acid2In solution, reacting 1.6h at 75 DEG C, to remove lignin, filter, filtering residue is extremely neutral with deionized water wash, standby；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1:5.7；The NaClO of described acidifying with acetic acid2The preparation method of solution is by NaClO2Joining quality is in its deionized water of 25 times, then with glacial acetic acid, pH is transferred to 3 again, to obtain final product；
C. being soaked in by the filtering residue obtained through step b process in the KOH aqueous solution that mass concentration is 2%, at room temperature react 24h, to remove hemicellulose, filter, filtering residue is extremely neutral with deionized water wash, standby；
D. repeat step c 3 times, obtain the powdered rubber of white；
E. being soaked in the KOH aqueous solution that mass concentration is 6% by the filtering residue (powdered rubber of white) obtained through step d process, react 2h at 80 DEG C, thoroughly to remove hemicellulose, filter, filtering residue is extremely neutral with deionized water wash, standby；
F. the filtering residue obtained through step e process is soaked in the hydrochloric acid that mass concentration is 1%, in 80 DEG C react 0.95h remove impurity, filter, filtering residue deionized water wash to neutrality, vacuum drying, obtain Bagasse-cellulose, i.e. native cellulose；
Step (2), a modification by copolymerization is propped up in connecing of native cellulose: the Bagasse-cellulose taking step (1) prepared joins in deionized water, after being warmed up to 110 DEG C under nitrogen atmosphere, add the potassium permanganate (initiator) that quality is Bagasse-cellulose 0.004% and carry out pre-oxidation, add acrylic acid after 40min and carry out graft copolymerization, after reaction 180min, add the Benzodiazepines aqueous solution (polymerization inhibitor) that mass concentration is 1.5%；Being carried out 3 times with the ethanol that volumetric concentration is 95%, sucking filtration, filtering residue deionized water cleans to neutrality, dry, obtains using modified bagasse cellulose again；
Wherein, Bagasse-cellulose is 1:20 with the solid-to-liquid ratio of deionized water；Bagasse-cellulose and acrylic acid solid-to-liquid ratio are 1:6；The solid-to-liquid ratio of Bagasse-cellulose and Benzodiazepines aqueous solution is 1:3；Bagasse-cellulose is 1:10 with each solid-to-liquid ratio cleaning required ethanol；
Step (3), load β type FeOOH: be immersed in the sodium hydrate aqueous solution of 3mol/L and carry out basification by the using modified bagasse cellulose that step (2) prepares, after 1h, add the iron powder that quality is Bagasse-cellulose quality 15%, and carry out stirring reaction 0.5h；Add the sodium hydrate aqueous solution of 2mol/L afterwards, after reaction 24h, filter, take filtering residue, be carried out to colourless with deionized water, dry at 60 DEG C, β type FeOOH modified natural fibers element functional type material must be loaded；
Wherein, Bagasse-cellulose is 1:3.5 with the solid-to-liquid ratio of the sodium hydrate aqueous solution of 2mol/L.
Embodiment 3
A kind of preparation method loading β type FeOOH modified natural fibers element functional type material, comprises the steps:
Step (1), the preparation of native cellulose:
A. bagasse is added to the mixed solvent of ethanol and toluene, stirring reaction 6.5h under room temperature, filter, with deionized water wash filtering residue to remove solvent；The solid-to-liquid ratio of bagasse and ethanol is 1:15；The solid-to-liquid ratio of bagasse and toluene is 1:6；
B. the filtering residue after a step being washed joins the NaClO of acidifying with acetic acid2In solution, reacting 2h at 76 DEG C, to remove lignin, filter, filtering residue is extremely neutral with deionized water wash, standby；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1:6；The NaClO of described acidifying with acetic acid2The preparation method of solution is by NaClO2Joining quality is in its deionized water of 26 times, then with glacial acetic acid, pH is transferred to 3 again, to obtain final product；
C. being soaked in by the filtering residue obtained through step b process in the KOH aqueous solution that mass concentration is 2%, at room temperature react 25h, to remove hemicellulose, filter, filtering residue is extremely neutral with deionized water wash, standby；
D. repeat step c 4 times, obtain the powdered rubber of white；
E. being soaked in the KOH aqueous solution that mass concentration is 6% by the filtering residue (powdered rubber of white) obtained through step d process, react 2.1h at 81 DEG C, thoroughly to remove hemicellulose, filter, filtering residue is extremely neutral with deionized water wash, standby；
F. the filtering residue obtained through step e process is soaked in the hydrochloric acid that mass concentration is 1%, in 81 DEG C react 1h remove impurity, filter, filtering residue deionized water wash to neutrality, vacuum drying, obtain Bagasse-cellulose, i.e. native cellulose；
Step (2), a modification by copolymerization is propped up in connecing of native cellulose: the Bagasse-cellulose taking step (1) prepared joins in deionized water, after being warmed up to 111 DEG C under nitrogen atmosphere, add the potassium permanganate (initiator) that quality is Bagasse-cellulose 0.006% and carry out pre-oxidation, add acrylic acid after 45min and carry out graft copolymerization, after reaction 185min, add the Benzodiazepines aqueous solution (polymerization inhibitor) that mass concentration is 12%；Being carried out 4 times with the ethanol that volumetric concentration is 95%, sucking filtration, filtering residue deionized water cleans to neutrality, dry, obtains using modified bagasse cellulose again；
Wherein, Bagasse-cellulose is 1:21 with the solid-to-liquid ratio of deionized water；Bagasse-cellulose and acrylic acid solid-to-liquid ratio are 1:10；The solid-to-liquid ratio of Bagasse-cellulose and Benzodiazepines aqueous solution is 1:4；Bagasse-cellulose is 1:11 with each solid-to-liquid ratio cleaning required ethanol；
Step (3), load β type FeOOH: be immersed in the sodium hydrate aqueous solution of 3mol/L and carry out basification by the using modified bagasse cellulose that step (2) prepares, after 1.1h, add the iron powder that quality is Bagasse-cellulose quality 20%, and carry out stirring reaction 0.55h；Add the sodium hydrate aqueous solution of 2mol/L afterwards, after reaction 25h, filter, take filtering residue, be carried out to colourless with deionized water, dry at 61 DEG C, β type FeOOH modified natural fibers element functional type material must be loaded；
Wherein, Bagasse-cellulose is 1:4 with the solid-to-liquid ratio of the sodium hydrate aqueous solution of 2mol/L.
Embodiment 4
As shown in Figure 1, a kind of arsenic-containing waste water processes system, including the aeration oxidation pool 1 being sequentially connected with, flocculation sedimentation tank 2, reactor and depositing reservoir 5, described reactor is built-in is filled with the loading β type FeOOH modified natural fibers element functional type material that embodiment 2 prepares, and forms filler 20.
Described reactor can be 1, it is possibility to have multiple, when for having only to time multiple be arranged in series.The present embodiment has 2 reactors, is the first reactor 3 and the second reactor 4.
Aeration oxidation pool 1 water inlet is provided with intake pump 6, the outlet of aeration oxidation pool 1 is connected with the water inlet of flocculation sedimentation tank 2 by the first valve 7, mud valve 8 it is provided with bottom flocculation sedimentation tank 2, the outlet of flocculation sedimentation tank 2 is connected with the water inlet bottom the first reactor 3 by the second valve 9, outlet bottom first reactor 3 is connected with the water inlet at the second reactor 4 top by the 3rd valve 10, and the outlet bottom the second reactor 4 is connected with the water inlet of depositing reservoir 5 by the 4th valve 11；
The bottom of depositing reservoir 5 is provided with blowoff valve 12；
The bottom of described aeration oxidation pool 1 is provided with aeration head 13, and described aeration head 13 is sequentially connected with gas flowmeter 14, aeration pump 15；Aeration pump 15 is also connected with the power output end of converter 16, and the power input of converter 16 all electrically connects with PLC17；
Being additionally provided with multiple dissolved oxygen electrode 18 in described aeration oxidation pool 1, these dissolved oxygen electrodes 18 are connected with the outfan of online dissolved oxygen instrument 19, and the input of online dissolved oxygen instrument 19 electrically connects with PLC17.The present embodiment has 2 dissolved oxygen electrodes 18.
Embodiment 5
A kind of method for treating arsenic-containing wastewater, selects Yunnan mountain of papers arsenicum factory arsenic-containing waste water, and influent concentration arsenic content is 128mg/L, pH is 4.5, uses the arsenic-containing waste water of embodiment 4 to process system and processes, and step is as follows:
Arsenic-containing waste water enters aeration oxidation pool through intake pump and carries out aerating oxidation 25min, and during aerating oxidation, controlling the dissolved oxygen value DO of arsenic-containing waste water in aeration oxidation pool is 2.6mg/L；
Arsenic-containing waste water through aerating oxidation enters into and carries out flocculation sediment in flocculation sedimentation tank；Arsenic content≤200mg/L, pH6-9 in flocculation sediment water inlet, the time of staying in arsenic-containing waste water flocculation sedimentation tank is 48min；It is 6-9 through the arsenic-containing waste water pH of flocculation sediment, arsenic content≤10mg/L；
Then being passed into by the arsenic-containing waste water through flocculation sediment in reactor and react, the response time is 30min；
In reacted device, the waste water entrance depositing reservoir clarification after reaction treatment can be discharged；Wherein the effective depth h of depositing reservoir is 1.8m, and during clarification, the time of staying HRT of waste water is 12h.
The flocculant adopted in described flocculation sedimentation tank is calcium hydroxide, and making consumption is 0.58mg/L.
Going out water monitoring arsenic concentration is 0.018mg/L, has reached existing discharge standard.
Embodiment 6
A kind of method for treating arsenic-containing wastewater, selects chemical plant, Yunnan arsenic-containing waste water, and influent concentration arsenic content is 85mg/L, pH is 5, uses the arsenic-containing waste water of embodiment 4 to process system and processes, and step is as follows:
Arsenic-containing waste water enters aeration oxidation pool through intake pump and carries out aerating oxidation 20min, and during aerating oxidation, controlling the dissolved oxygen value DO of arsenic-containing waste water in aeration oxidation pool is 2mg/L；
Arsenic-containing waste water through aerating oxidation enters into and carries out flocculation sediment in flocculation sedimentation tank；Arsenic content≤200mg/L, pH6-9 in flocculation sediment water inlet, the time of staying in arsenic-containing waste water flocculation sedimentation tank is 45min；It is 6-9 through the arsenic-containing waste water pH of flocculation sediment, arsenic content≤10mg/L；
Then being passed into by the arsenic-containing waste water through flocculation sediment in reactor and react, the response time is 28min；
In reacted device, the waste water entrance depositing reservoir clarification after reaction treatment can be discharged；Wherein the effective depth h of depositing reservoir is 1.5m, and during clarification, the time of staying HRT of waste water is 11h.
The flocculant adopted in described flocculation sedimentation tank is calcium hydroxide, and making consumption is 0.5mg/L.
Going out water monitoring arsenic concentration is 0.019mg/L, has reached 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 is 4, uses the arsenic-containing waste water of embodiment 4 to process system and processes, and step is as follows:
Arsenic-containing waste water enters aeration oxidation pool through intake pump and carries out aerating oxidation 30min, and during aerating oxidation, controlling the dissolved oxygen value DO of arsenic-containing waste water in aeration oxidation pool is 4mg/L；
Arsenic-containing waste water through aerating oxidation enters into and carries out flocculation sediment in flocculation sedimentation tank；Arsenic content≤200mg/L, pH6-9 in flocculation sediment water inlet, the time of staying in arsenic-containing waste water flocculation sedimentation tank is 50min；It is 6-9 through the arsenic-containing waste water pH of flocculation sediment, arsenic content≤10mg/L；
Then being passed into by the arsenic-containing waste water through flocculation sediment in reactor and react, the response time is 33min；
In reacted device, the waste water entrance depositing reservoir clarification after reaction treatment can be discharged；Wherein the effective depth h of depositing reservoir is 2m, and during clarification, the time of staying HRT of waste water is 13h.
The flocculant adopted in described flocculation sedimentation tank is calcium hydroxide, and making consumption is 0.65mg/L.
Going out water monitoring arsenic concentration is 0.02mg/L, has reached existing discharge standard.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.Skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; described in above-described embodiment and description is that principles of the invention is described; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements both fall within the claimed scope of the invention.Claimed scope is defined by appending claims and equivalent thereof.
Claims (10)
1. the preparation method loading β type FeOOH modified natural fibers element functional type material, it is characterised in that comprise the steps:
Step (1), the preparation of native cellulose:
A. bagasse is added to the mixed solvent of ethanol and toluene, stirring reaction 5.5-6.5h under room temperature, filter, with deionized water wash filtering residue to remove solvent；The solid-to-liquid ratio of bagasse and ethanol is 1:10-15；The solid-to-liquid ratio of bagasse and toluene is 1:4-6；
B. the filtering residue after a step being washed joins the NaClO of acidifying with acetic acid2In solution, reacting 1.5-2h, filter at 74-76 DEG C, filtering residue is extremely neutral with deionized water wash, standby；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1:5.5-6；The NaClO of described acidifying with acetic acid2The preparation method of solution is by NaClO2Joining quality is in its deionized water of 24-26 times, then with glacial acetic acid, pH is transferred to 3 again, to obtain final product；
C. being soaked in by the filtering residue obtained through step b process in the KOH aqueous solution that mass concentration is 2%, at room temperature react 23-25h, filter, filtering residue is extremely neutral with deionized water wash, standby；
D. step c 3-4 time is repeated；
E. being soaked in by the filtering residue obtained through step d process in the KOH aqueous solution that mass concentration is 6%, react 1.9-2.1h at 79-81 DEG C, filter, filtering residue is extremely neutral with deionized water wash, standby；
F. the filtering residue obtained through step e process is soaked in the hydrochloric acid that mass concentration is 1%, in 79-81 DEG C react 0.9-1h, filter, filtering residue deionized water wash to neutrality, vacuum drying, obtain Bagasse-cellulose, i.e. native cellulose；
Step (2), a modification by copolymerization is propped up in connecing of native cellulose: the Bagasse-cellulose taking step (1) prepared joins in deionized water, after being warmed up to 109-111 DEG C under nitrogen atmosphere, add the potassium permanganate that quality is Bagasse-cellulose 0.002%-0.006% and carry out pre-oxidation, add acrylic acid after 30-45min and carry out graft copolymerization, after reaction 175-185min, add the Benzodiazepines aqueous solution that mass concentration is 1-2%；Being carried out 2-4 time with the ethanol that volumetric concentration is 95%, sucking filtration, filtering residue deionized water cleans to neutrality, dry, obtains using modified bagasse cellulose again；
Wherein, Bagasse-cellulose is 1:19-21 with the solid-to-liquid ratio of deionized water；Bagasse-cellulose and acrylic acid solid-to-liquid ratio are 1:4-10；The solid-to-liquid ratio of Bagasse-cellulose and Benzodiazepines aqueous solution is 1:2-4；Bagasse-cellulose is 1:9-11 with each solid-to-liquid ratio cleaning required ethanol；
Step (3), load β type FeOOH: be immersed in the sodium hydrate aqueous solution of 3mol/L and carry out basification by the using modified bagasse cellulose that step (2) prepares, after 0.9-1.1h, add the iron powder that quality is Bagasse-cellulose quality 10-20%, and carry out stirring reaction 0.45-0.55h；Add the sodium hydrate aqueous solution of 2mol/L afterwards, after reaction 23-25h, filter, take filtering residue, be carried out to colourless with deionized water, dry at 59-61 DEG C, β type FeOOH modified natural fibers element functional type material must be loaded；
Wherein, Bagasse-cellulose is 1:3-4 with the solid-to-liquid ratio of the sodium hydrate aqueous solution of 2mol/L.
2. the preparation method loading β type FeOOH modified natural fibers element functional type material according to claim 1, it is characterised in that comprise the steps:
Step (1), the preparation of native cellulose:
A. bagasse is added to the mixed solvent of ethanol and toluene, stirring reaction 5h under room temperature, filter, with deionized water wash filtering residue to remove solvent；The solid-to-liquid ratio of bagasse and ethanol is 1:12；The solid-to-liquid ratio of bagasse and toluene is 1:5；
B. the filtering residue after a step being washed joins the NaClO of acidifying with acetic acid2In solution, reacting 1.6h, filter at 75 DEG C, filtering residue is extremely neutral with deionized water wash, standby；The NaClO of bagasse and acidifying with acetic acid2The solid-to-liquid ratio of solution is 1:5.7；The NaClO of described acidifying with acetic acid2The preparation method of solution is by NaClO2Joining quality is in its deionized water of 25 times, then with glacial acetic acid, pH is transferred to 3 again, to obtain final product；
C. being soaked in by the filtering residue obtained through step b process in the KOH aqueous solution that mass concentration is 2%, at room temperature react 24h, filter, filtering residue is extremely neutral with deionized water wash, standby；
D. step c 3 times are repeated；
E. being soaked in by the filtering residue obtained through step d process in the KOH aqueous solution that mass concentration is 6%, react 2h at 80 DEG C, filter, filtering residue is extremely neutral with deionized water wash, standby；
F. the filtering residue obtained through step e process is soaked in the hydrochloric acid that mass concentration is 1%, in 80 DEG C react 0.95h, filter, filtering residue deionized water wash to neutrality, vacuum drying, obtain Bagasse-cellulose, i.e. native cellulose；
Step (2), a modification by copolymerization is propped up in connecing of native cellulose: the Bagasse-cellulose taking step (1) prepared joins in deionized water, after being warmed up to 110 DEG C under nitrogen atmosphere, add the potassium permanganate that quality is Bagasse-cellulose 0.004% and carry out pre-oxidation, add acrylic acid after 40min and carry out graft copolymerization, after reaction 180min, add the Benzodiazepines aqueous solution that mass concentration is 1.5%；Being carried out 3 times with the ethanol that volumetric concentration is 95%, sucking filtration, filtering residue deionized water cleans to neutrality, dry, obtains using modified bagasse cellulose again；
Wherein, Bagasse-cellulose is 1:20 with the solid-to-liquid ratio of deionized water；Bagasse-cellulose and acrylic acid solid-to-liquid ratio are 1:6；The solid-to-liquid ratio of Bagasse-cellulose and Benzodiazepines aqueous solution is 1:3；Bagasse-cellulose is 1:10 with each solid-to-liquid ratio cleaning required ethanol；
Step (3), load β type FeOOH: be immersed in the sodium hydrate aqueous solution of 3mol/L and carry out basification by the using modified bagasse cellulose that step (2) prepares, after 1h, add the iron powder that quality is Bagasse-cellulose quality 15%, and carry out stirring reaction 0.5h；Add the sodium hydrate aqueous solution of 2mol/L afterwards, after reaction 24h, filter, take filtering residue, be carried out to colourless with deionized water, dry at 60 DEG C, β type FeOOH modified natural fibers element functional type material must be loaded；
Wherein, Bagasse-cellulose is 1:3.5 with the solid-to-liquid ratio of the sodium hydrate aqueous solution of 2mol/L.
3. the loading β type FeOOH modified natural fibers element functional type material that the preparation method loading β type FeOOH modified natural fibers element functional type material described in claim 1 or 2 prepares.
4. what the preparation method loading β type FeOOH modified natural fibers element functional type material described in claim 1 or 2 prepared loads the application in water processes of the β type FeOOH modified natural fibers element functional type material.
5. what the preparation method loading β type FeOOH modified natural fibers element functional type material described in claim 1 or 2 prepared loads the application in arsenic-containing waste water processes of the β type FeOOH modified natural fibers element functional type material.
6. an arsenic-containing waste water processes system, it is characterized in that: include the aeration oxidation pool, flocculation sedimentation tank, reactor and the depositing reservoir that are sequentially connected with, described reactor is built-in is filled with the loading β type FeOOH modified natural fibers element functional type material that claim 1 prepares.
7. arsenic-containing waste water according to claim 6 processes system, it is characterised in that: described reactor has multiple, and is arranged in series.
8. arsenic-containing waste water according to claim 6 processes system, it is characterised in that: described reactor has 2, i.e. the first reactor and the second reactor；
Aeration oxidation pool water inlet is provided with intake pump, the outlet of aeration oxidation pool is connected with the water inlet of flocculation sedimentation tank by the first valve, mud valve it is provided with bottom flocculation sedimentation tank, the outlet of flocculation sedimentation tank is connected by the water inlet of the second valve and the first reactor bottom, the outlet of the first reactor bottom is connected by the water inlet of the 3rd valve and the second reactor head, and the outlet of the second reactor bottom is connected with the water inlet of depositing reservoir by the 4th valve；
The bottom of depositing reservoir is provided with blowoff valve；
The bottom of described aeration oxidation pool is provided with aeration head, and described aeration head and gas flowmeter, aeration pump are sequentially connected；Aeration pump is also connected with the power output end of converter, and the power input of converter all electrically connects with PLC；
Being additionally provided with multiple dissolved oxygen electrode in described aeration oxidation pool, these dissolved oxygen electrodes are connected with the outfan of online dissolved oxygen instrument, and the input of online dissolved oxygen instrument electrically connects with PLC.
9. a method for treating arsenic-containing wastewater, uses the arsenic-containing waste water described in claim 6-8 any one to process system and processes, it is characterised in that 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, controlling the dissolved oxygen value DO of arsenic-containing waste water in aeration oxidation pool is 2-4mg/L；
Arsenic-containing waste water through aerating oxidation enters into and carries out flocculation sediment in flocculation sedimentation tank；Arsenic content≤200mg/L, pH6-9 in flocculation sediment water inlet, the time of staying in arsenic-containing waste water flocculation sedimentation tank is 45-50min；It is 6-9 through the arsenic-containing waste water pH of flocculation sediment, arsenic content≤10mg/L；
Then being passed into by the arsenic-containing waste water through flocculation sediment in reactor and react, the response time is 28-33min；
In reacted device, the waste water entrance depositing reservoir clarification after reaction treatment can be discharged；Wherein the effective depth h of depositing reservoir is 1.5-2m, and during clarification, the time of staying HRT of waste water is 11-13h.
10. method for treating arsenic-containing wastewater according to claim 9, it is characterised in that the flocculant adopted in described flocculation sedimentation tank is calcium hydroxide, and making consumption is 0.5-0.65mg/L.
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