CN104828895B - A kind of method for treating water of enzymolysis xylogen using oxidation modified zirconia - Google Patents
A kind of method for treating water of enzymolysis xylogen using oxidation modified zirconia Download PDFInfo
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- CN104828895B CN104828895B CN201510207221.0A CN201510207221A CN104828895B CN 104828895 B CN104828895 B CN 104828895B CN 201510207221 A CN201510207221 A CN 201510207221A CN 104828895 B CN104828895 B CN 104828895B
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- enzymolysis xylogen
- modified zirconia
- fluorine
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- oxidation modified
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Abstract
The invention discloses the method for the phosphorus in a kind of enzymolysis xylogen Adsorption water body for aoxidizing modified zirconia and fluorine, pretreated enzymolysis xylogen is highly dispersed in organic solvent dimethyl sulfoxide (DMSO), organic zirconium source is used as using zirconium-n-propylate, oxidation modified zirconia is carried out to enzymolysis xylogen using hydrothermal synthesis method, the enzymolysis xylogen of oxidation modified zirconia is prepared；The enzymolysis xylogen for aoxidizing modified zirconia is added in phosphorous or fluorine-containing water body, phosphorus or fluorine in Adsorption water body.The present invention is applied in the processing of phosphorous fluorine-containing water body first using the material as adsorbent.The adsorbent shows the removal effect good to phosphorus and fluorine, and enzymolysis xylogen is biomass resource, renewable, is the waste residue of biomass energy technique, and wide material sources are inexpensive, and the purpose of the treatment of wastes with processes of wastes against one another can be achieved；And absorption is time-consuming short, treatment conditions are gentle, and treatment effeciency is high.The present invention, which is applied to remove phosphorus and fluorine in water body, has good economy and environmental benefit.
Description
Technical field
The invention belongs to water-treatment technology field, it is related to the minimizing technology of orthophosphates and/or fluorine ion in a kind of water body,
Specifically related to a kind of orthophosphates and/or fluorine using in the enzymolysis xylogen material Adsorption sanitary sewage for aoxidizing modified zirconia
The method of ion.
Background technology
Water body eutrophication and high fluorination caused by fluoride pollution caused by phosphorus pollutes, directly influence drinking for people
Water security so that China's freshwater resources are more and more deficienter.
Compared to elemental nitrogen, phosphorus is to cause body eutrophication more crucial restrictive factor, and main source has two sides
Face, one is endogenous pollution, such as phosphorus of water body itself bed mud deposit release etc.；One is external source pollution, such as sanitary sewage and work
The pollution of area source such as the point-source pollutions such as industry waste water and farmland are washed away, fish-pond.And if excess intake fluorine can produce fluorine spot in human body
The illness such as tooth and fluorosis of bone, can more cause skin burn, dermatitis and respiratory inflammation etc. during high concentration.The source of high-fluorine water except
Outside natural factor, electronics industry, glass industry, pickling waste waters and for smeltery, thermal power plant and rubbish are mainly derived from
The washing tail gas waste water of rubbish treatment plant etc..At present, the technology of domestic and international dephosphorization fluorine removal mainly has chemical method, ion-exchange, electricity
Chemical method and absorption method etc., wherein absorption method turn into study hotspot as a kind of method of efficient low-consume energy；Conventional dephosphorization is inhaled
Attached dose of active charcoal, flyash, slag, metal oxide and its composite etc., conventional de-fluoridation adsorbent have clay, boiling
Stone, bentonite, bone black and activated alumina etc..
Enzymolysis xylogen is a kind of reproducible biomass resource, it extract from using microorganism enzymolysis cereal, stalk and
Other agricultural wastes carry out the residue in the preparation of energy fuel, and its rich content such as digests maize straw system in microorganism
Enzymolysis xylogen containing 40-50% in the residue of standby energy ethanol.It is living containing substantial amounts of aldehyde radical and hydroxyl etc. in lignin molecule
Property functional group, is conducive to being chemically modified on its surface, modification and the phenol formaldehyde foam of polyurethane foam is mainly used at present
Synthesis of material etc..Research has shown that, zirconium oxide has certain selection characterization of adsorption to phosphorus and fluorine, in order to widen lignin life
The application fields of physical resources, accelerate higher value application to fermentation residue main component lignin, realize sustainable development and
Zirconium oxide is carried on the material surface of enzymolysis xylogen and for orthophosphates and fluorine ion in water body by environmental protection, this patent
Adsorption.
Enzymolysis xylogen be applied to the Adsorption of phosphorus and fluorine in water body, at present not yet after zirconium oxide modification
See relevant report.
The content of the invention
1. the technical problem to be solved
For the available effective active adsorption site of zirconium oxide is limited, adsorbent cost is higher, the absorption of dephosphorization fluorine removal
The not high defect of amount removes phosphorus in water body and/or fluorine there is provided a kind of enzymolysis xylogen for aoxidizing modified zirconia as adsorbent
Method.
2. technical scheme
The present invention uses the method for treating water of the enzymolysis xylogen of oxidation modified zirconia, to aoxidize the enzymolysis xylogen of modified zirconia
As adsorbent, orthophosphates and/or fluorine ion in Adsorption water body.
The method for treating water of the above-mentioned enzymolysis xylogen using oxidation modified zirconia, specifically includes following steps：
The purification of step 1, enzymolysis xylogen：
Enzymolysis xylogen is according to mass volume ratio 1g：10ml is dissolved into the sodium hydrate aqueous solution that pH is 9.0 ~ 10.0,
Agitation and filtration, it is 2.0 ~ 3.0 that filtrate, which is adjusted to pH with hydrochloric acid solution, is filtered again after stirring, and filter cake is washed to neutrality, drying to perseverance
Weight, obtains pretreated enzymolysis xylogen；
The preparation of step 2, the enzymolysis xylogen of oxidation modified zirconia：
Pretreated enzymolysis xylogen made from step 1 is dissolved in dimethyl sulfoxide (DMSO), 70 wt.% zirconium-n-propylates are added
Solution, carries out zirconium reaction, washing, dry, the enzymolysis xylogen of acquisition oxidation modified zirconia after reaction product cooling；
Step 3, adsorption and dephosphorization fluorine removal：
The enzymolysis xylogen of the obtained oxidation modified zirconia of step 2 is added in staying water, Adsorption orthophosphates
And/or fluorine ion.
In the method for treating water of the above-mentioned enzymolysis xylogen using oxidation modified zirconia, in step 1, pH is 9.0 ~ 10.0
Sodium hydrate aqueous solution is formed using 20 wt.% sodium hydroxide solution regulation, the salt that described hydrochloric acid solution is 10 wt.%
Acid solution.
In the method for treating water of the above-mentioned enzymolysis xylogen using oxidation modified zirconia, the zirconiumization reaction described in step 2
In, the mass ratio of enzymolysis xylogen and zirconium-n-propylate is 1:1.5~6.
In the method for treating water of the above-mentioned enzymolysis xylogen using oxidation modified zirconia, the zirconiumization reaction described in step 2
Temperature is 110~140 DEG C, and the reaction time is 3~5 h.
In the method for treating water of the above-mentioned enzymolysis xylogen using oxidation modified zirconia, the zirconiumization reaction described in step 2
Carry out in an inert atmosphere.
In the method for treating water of the above-mentioned enzymolysis xylogen using oxidation modified zirconia, the reaction product described in step 2
Washed respectively using n-hexane, dimethyl sulfoxide (DMSO), absolute ethyl alcohol and water successively, after washing under the conditions of 60~80 DEG C vacuum
Dry.
In the method for treating water of the above-mentioned enzymolysis xylogen using oxidation modified zirconia, it is 2 that described water body, which contains phosphorus concentration,
~17 P mg/L, fluoro-containing concentration is 2~17 F mg/L.
In the method for treating water of the above-mentioned enzymolysis xylogen using oxidation modified zirconia, described adsorption time is 48~72
H, adsorption temp is 25~65 DEG C.
3. beneficial effect
Compared to prior art, the advantage of the invention is that：
1st, the enzymolysis xylogen surface of the oxidized modified zirconia of use hydro-thermal method of the invention has the oxidation of high degree of dispersion
Zirconium nano-particle；Show through adsorption experiment, modified enzymolysis xylogen all has certain adsorption effect, and effect to phosphorus and fluorine
Fruit more increased.More passing product has and significantly improved on adsorption effect, under equal conditions, the adsorbance of phosphorus
It is significantly better than bentonite and carries the suctions such as zirconium (8.96 mg/g), ceramics load zirconium (8.49 mg/g) and attapulgite load zirconium (7.1 mg/g)
Enclosure material, the adsorbance of fluorine is significantly better than silica gel and carries zirconium (4.20mg/g), zeolite load zirconium (4.70 mg/g) and gel load zirconium
Sorbing materials such as (4.10mg/g).
2nd, conventional art, the mode for loading zirconium is more using zirconium oxychloride as inorganic zirconium source, using infusion process or coprecipitation
It is prepared from, the sorbing material thus prepared often has the not high defect of activated adoption site zirconium utilization rate；And this hair
Mainly using zirconium-n-propylate as organic zirconium source in bright, it is prepared from using the method for rear grafting, activated zr is deposited with Zr-OH forms
, and material surface can be evenly distributed on, more adsorption sites are exposed, adsorption effect is substantially increased.
3rd, in addition, when the phosphorus and fluorine in modified enzymolysis xylogen simultaneously adsorbed water body, the removal effect to phosphorus is
Effect during better than independent Phosphate Sorption, and fluorine is then opposite.Phosphorus and fluorine are adsorbed simultaneously when, phosphorus and fluorine are modified in zirconium oxide
There is competitive Adsorption in the activated adoption site on enzymolysis xylogen surface, and be facilitation to the absorption of phosphorus, and to fluorine be suppression
Make and use.In addition, research shows, rise temperature and increase ionic strength can effectively improve phosphorus during phosphorus in independent adsorbed water body
Removal efficiency.
4th, matrix material enzymolysis xylogen is a kind of biological material in the adsorbent that the present invention is used, and the material can be again
Raw, wide material sources are the waste residues for preparing biomass energy, cheap；To phosphorus and the treatment effect of fluorine after oxidized modified zirconia
Significantly.
5th, in addition, the inventive method adsorption treatment mild condition, time-consuming short, water treatment efficiency can be greatly improved.Therefore, will
The enzymolysis xylogen of modified zirconia is aoxidized applied to the phosphorus and fluorine in Adsorption water body, with good economy and environmental benefit.
Brief description of the drawings
Fig. 1 be zirconium oxide before modified after enzymolysis xylogen the full spectrograms of XPS.
Fig. 2 be zirconium oxide before modified after enzymolysis xylogen FTIR figure.
It is modified Zr3d and Zr3p peaks occur on enzymolysis xylogen surface as shown in Fig. 1 in accompanying drawing, show zirconium oxide into
Work(is supported on enzymolysis xylogen surface.In accompanying drawing Fig. 2 be zirconium oxide before modified after material Fourier's infrared spectrum result, such as scheme
Shown, enzymolysis xylogen is in 1708cm after oxidized modified zirconia-1C=O stretching vibration peaks at place disappear, while in 951cm-1Place goes out
An existing new Zr absworption peak, result above shows that zirconium oxide is formed by occurring interaction with the oxygen-containing functional group on surface
Work(is supported on enzymolysis xylogen.
Embodiment
With reference to embodiment, the present invention will be described in detail.Changed in described specific embodiment with zirconium oxide
Property enzymolysis xylogen as adsorbent, Adsorption is carried out to the phosphorus in water body and fluorine, absorption is using static batch processed mistake
Journey.But implement the concrete mode of the invention being not limited to described in embodiment, any those skilled in the art,
In the scope of the invention, make change using disclosed technology contents or change, so as to obtain the essentially identical implementation of effect
Mode or method.In every case be objective without departing from technical solution of the present invention, any modification made to the embodiment, it is equivalent or
Equivalent change and modification, in the range of still falling within technical solution of the present invention.The scope of the present invention is not with specific embodiment party
Formula is limited, and is defined in the claims.
Embodiment 1
Step 1, take 20 wt.% sodium hydroxide solution adjust to pH be 9.0-10.0,10.0 g enzymolysis xylogens are molten
Solution enters wherein, is filtered after being sufficiently stirred for, and collects filtrate, then it is 2.0-3.0 to be adjusted to pH with 10 wt.% hydrochloric acid solution, is fully stirred
Filtered again after mixing, collect filter cake and it is fully washed to neutrality, it is standby to constant weight in vacuum drying at 40 DEG C, passed through
The enzymolysis xylogen of pretreatment, is denoted as BBL.
Step 2, take 1.0 gBBL to be distributed in 30 ml organic solvent dimethyl sulfoxide (DMSO)s, be stirred well to after being completely dissolved,
It is slowly added to the wt.% of 3 ml 70 zirconium-n-propylate solution（Positive methanol zirconium quality is 3.17g herein）, in 110~140 DEG C of conditions
The lower progress h of hydro-thermal reaction 3~5, reaction terminates to filter after natural cooling, successively using n-hexane, dimethyl sulfoxide (DMSO), anhydrous
Ethanol and water are fully washed respectively, are finally dried in vacuo at 60~80 DEG C, obtain the enzymolysis xylogen of oxidation modified zirconia,
It is denoted as BBL-Zr.
Embodiment 2
The enzymolysis xylogen BBL-Zr of the oxidation modified zirconia synthesized using in embodiment 1 is adsorbent, the phosphorous water of adsorption treatment
Body.Specific adsorption treatment process is as follows：Static Adsorption is carried out in the EPA bottles that 40 mL have tetrafluoroethene pad, adsorbent is with containing
The optional scope of mass ratio of phosphoric acid body of salt is 1:800 ~ 2000, the ratio selected in the present embodiment is 1:2000, pH=6.0 ±
0.2, phosphorus initial concentration is 14.89 mg/L, and NaCl and fluorine ion are free of in water body, and adsorption temp is 25 DEG C, and adsorption time is 24
h.After adsorption equilibrium, the aqueous phase filter through 45 μ L is filtered, and the concentration of phosphorus is surveyed using molybdenum blue colorimetric method at 700nm in filtrate
It is fixed.Measure adsorbance（In terms of phosphorus）For 13.70 mg/g.
Embodiment 3
The enzymolysis xylogen preparation method be the same as Example 1 of modified zirconia is aoxidized, wherein the quality for adding positive methanol zirconium is 1.587
G, adsorption conditionses be the same as Example 2, finally the adsorbance to phosphorus is 4.03 mg/g.
Embodiment 4
The enzymolysis xylogen preparation method be the same as Example 1 of modified zirconia is aoxidized, wherein the quality for adding positive methanol zirconium is 6.348
G, adsorption conditionses be the same as Example 2, finally the adsorbance to phosphorus is 15.44 mg/g.
It can be seen that, the quality of increase active component zirconium can effectively improve the removal effect of phosphorus in water body.
Embodiment 5
Aoxidize the enzymolysis xylogen preparation method be the same as Example 1 of modified zirconia, adsorption conditionses be the same as Example 2, wherein absorption temperature
Spend for 45 DEG C, final adsorbent is 15.67 mg/g to the adsorbance of phosphorus.
Embodiment 6
Aoxidize the enzymolysis xylogen preparation method be the same as Example 1 of modified zirconia, adsorption conditionses be the same as Example 2, wherein absorption temperature
Spend for 65 DEG C, final adsorbent is 18.34 mg/g to the adsorbance of phosphorus.
It can be seen that, adsorption temp, which is 25 ~ 65 DEG C, preferable removal effect, improves adsorption temp and is conducive to phosphatic suction
It is attached to remove.
Embodiment 7
Aoxidize the enzymolysis xylogen preparation method be the same as Example 1 of modified zirconia, adsorption conditionses be the same as Example 2, containing in phosphorus water
NaCl containing 0.1 mol/L, is 14.35 mg/g to phosphatic Adsorption amount.
Embodiment 8
Aoxidize the enzymolysis xylogen preparation method be the same as Example 1 of modified zirconia, adsorption conditionses be the same as Example 2, containing in phosphorus water
NaCl containing 1.0 mol/L, is 20.40 mg/g to phosphatic Adsorption amount.
It can be seen that, improve Adsorption of the enzymolysis xylogen to phosphorus that the ionic strength in water body is conducive to aoxidizing modified zirconia.
Embodiment 9
Aoxidize in the enzymolysis xylogen preparation method be the same as Example 1 of modified zirconia, adsorption conditionses be the same as Example 2, water body at the beginning of fluorine
Beginning concentration is 16.45 mg/L, and NaCl and phosphorus are free of in water body, and the adsorbance to fluorine is 9.18 mg/g.
It can be seen that, aoxidize the enzymolysis xylogen of modified zirconia equally has certain removal effect to the fluorine in water body.
Embodiment 10
Aoxidize in the enzymolysis xylogen preparation method be the same as Example 1 of modified zirconia, adsorption conditionses be the same as Example 2, water body at the beginning of phosphorus
Beginning concentration is 14.19 mg/L, and fluorine initial concentration is 15.84 mg/L, and NaCl is free of in water body, and the adsorbance to phosphorus is 15.75
Mg/g, the adsorbance to fluorine is followed successively by 6.64 mg/g.
It can be seen that, when phosphorus in water body and fluorine simultaneously in the presence of, the activity on the modified enzymolysis xylogen surface of zirconium oxide is inhaled
Attached site generates competitive Adsorption, absorption as a result, the absorption to phosphorus is facilitation, be then inhibitory action to fluorine.
Claims (8)
1. a kind of method for treating water of enzymolysis xylogen using oxidation modified zirconia, it is characterised in that：To aoxidize the enzyme of modified zirconia
Lignin is solved as adsorbent, orthophosphates and/or fluorine ion in Adsorption water body；
Specifically include following steps：
The purification of step 1, enzymolysis xylogen：
Enzymolysis xylogen is dissolved into according to mass volume ratio 1g: 10ml in the sodium hydrate aqueous solution that pH is 9.0~10.0, stirring
Filtering, it is 2.0~3.0 that filtrate, which is adjusted to pH with hydrochloric acid solution, is filtered again after stirring, and filter cake is washed to neutrality, is dried to constant weight,
Obtain pretreated enzymolysis xylogen；
The preparation of step 2, the enzymolysis xylogen of oxidation modified zirconia：
Pretreated enzymolysis xylogen made from step 1 is dissolved in dimethyl sulfoxide (DMSO), 70wt.% zirconium-n-propylates are added molten
Liquid, carries out zirconium reaction, washing, dry, the enzymolysis xylogen of acquisition oxidation modified zirconia after reaction product cooling；
Step 3, adsorption and dephosphorization fluorine removal：
The enzymolysis xylogen of the obtained oxidation modified zirconia of step 2 is added in staying water, Adsorption orthophosphates and/or
Fluorine ion.
2. the method for treating water of the enzymolysis xylogen according to claim 1 using oxidation modified zirconia, it is characterised in that：Step
In rapid 1, pH for 9.0~10.0 sodium hydrate aqueous solution is formed using 20wt.% sodium hydroxide solution regulation, described
Hydrochloric acid solution is 10wt.% hydrochloric acid solution.
3. the method for treating water of the enzymolysis xylogen according to claim 1 using oxidation modified zirconia, it is characterised in that：Step
In zirconiumization reaction described in rapid 2, the mass ratio of enzymolysis xylogen and zirconium-n-propylate is 1: 1.5~6.
4. the method for treating water of the enzymolysis xylogen according to claim 1 using oxidation modified zirconia, it is characterised in that：Step
Zirconium reaction temperature described in rapid 2 is 110~140 DEG C, and the reaction time is 3~5h.
5. the method for treating water of the enzymolysis xylogen according to claim 1 using oxidation modified zirconia, it is characterised in that：Step
Zirconiumization reaction described in rapid 2 is carried out in an inert atmosphere.
6. the method for treating water of the enzymolysis xylogen according to claim 1 using oxidation modified zirconia, it is characterised in that：Step
Reaction product described in rapid 2 is washed respectively using n-hexane, dimethyl sulfoxide (DMSO), absolute ethyl alcohol and water successively, after washing
It is dried in vacuo under the conditions of 60~80 DEG C.
7. the method for treating water of the enzymolysis xylogen according to claim 1 using oxidation modified zirconia, it is characterised in that：Institute
The water body stated is 2~17P mg/L containing phosphorus concentration, and fluoro-containing concentration is 2~17F mg/L.
8. the method for treating water of the enzymolysis xylogen according to claim 1 using oxidation modified zirconia, it is characterised in that：Institute
The adsorption time stated is 48~72h, and adsorption temp is 25~65 DEG C.
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