CN104828895A - Water treatment method using zirconia modified enzymatic hydrolysis lignin - Google Patents
Water treatment method using zirconia modified enzymatic hydrolysis lignin Download PDFInfo
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Abstract
The invention discloses a method using zirconia modified enzymatic hydrolysis lignin to remove phosphor and fluorine in water through adsorption. The zirconia modified enzymatic hydrolysis lignin is prepared by the following steps: preprocessing enzymatic hydrolysis lignin, then highly dispersing enzymatic hydrolysis lignin in an organic solvent (dimethyl sulfoxide), taking n-propanol zirconium as the organic zirconium source, carrying out zirconia modification on enzymatic hydrolysis lignin through a hydrothermal synthesis method so as to obtain the zirconia modified enzymatic hydrolysis lignin, which can be directly added into water containing phosphor or fluorine to remove the phosphor or fluorine. The provided lignin is taken as an absorbent for the first time and is applied to treatment on water containing phosphor or fluorine. The absorbent has a good effect on eliminating phosphor and fluorine; the enzymatic hydrolysis lignin is a biomass resource, can be regenerated, and is dregs in the biomass energy technology; the resource of enzymatic hydrolysis lignin is wide, the price is cheap, and the waste can be converted into valuable resource. The adsorption time is short, the treatment conditions are mild, and the processing efficiency is high. The provided lignin can be used to remove phosphor and fluorine in water and is capable of creating good economic and environmental benefits.
Description
Technical field
The invention belongs to water-treatment technology field, relate to the minimizing technology of orthophosphoric acid salt and/or fluorion in a kind of water body, be specifically related to a kind of method that enzymolysis xylogen materials adsorption utilizing zirconium white modification removes orthophosphoric acid salt in sanitary sewage and/or fluorion.
Background technology
The eutrophication that water body causes because phosphorus pollutes and the height caused because of fluoride pollution are fluoridized, and directly have influence on the drinking water safety of people, make China's Freshwater resources more and more deficienter.
Compared to elemental nitrogen, phosphorus is the restrictive factor causing body eutrophication more crucial, and main source has two aspects, and one is endogenous pollution, as the phosphorus etc. of the settling releases such as water body self bed mud; One is that external source is polluted, as the point-source pollution such as sanitary sewage and trade effluent and farmland wash away, the pollution of area source such as fish-pond.And if excess intake fluorine can produce the illness such as dental fluorosis and osteofluorosis in human body, more skin burn, dermatitis and respiratory inflammation etc. can be caused during high density.The source of water of high fluorine content, except natural factor, is mainly derived from electronic industry, glass industry, pickling waste waters and the washing tail gas waste water for smeltery, fuel-burning power plant and destructor plant etc.At present, the technology that domestic and international dephosphorization removes fluorine mainly contains chemical method, ion exchange method, electrochemical process and absorption method etc., and wherein absorption method becomes study hotspot as a kind of method of efficient low-consume energy; Conventional dephosphorization adsorbent has gac, flyash, slag, metal oxide and matrix material thereof etc., and conventional de-fluoridation adsorbent has clay, zeolite, wilkinite, bone black and activated alumina etc.
Enzymolysis xylogen is a kind of reproducible biomass resource, its extracts the residue from utilizing microorganism enzymolysis cereal, stalk and other agricultural wastes to carry out in the preparation of energy fuel, its rich content, as prepared the enzymolysis xylogen containing 40-50% in the residue of energy ethanol at microorganism enzymolysis maize straw.Containing a large amount of aldehyde radicals and hydroxyl isoreactivity functional group in lignin molecule, be conducive to carrying out chemically modified on its surface, be mainly used in the modification of polyurethane foam and the synthesis etc. of phenolic foam material at present.Show after deliberation, zirconium white has certain adsorption selection characteristic to phosphorus and fluorine, in order to widen lignin matter resource Application Areas, accelerate higher value application to fermentation residue main component xylogen, realize Sustainable development and environmental protection, zirconium white is carried on the material surface of enzymolysis xylogen and is used for the Adsorption of orthophosphoric acid salt and fluorion in water body by this patent.
Be applied to the Adsorption of phosphorus and fluorine in water body after enzymolysis xylogen is carried out zirconium white modification, have not yet to see relevant report.
Summary of the invention
1. the technical problem that will solve
, dephosphorization higher for zirconium white available effective active adsorption site cost that is limited, sorbent material, except the not high defect of fluorine adsorptive capacity, provides a kind of enzymolysis xylogen of zirconium white modification to remove the method for phosphorus in water body and/or fluorine as sorbent material.
2. technical scheme
The present invention adopts the water treatment method of the enzymolysis xylogen of zirconium white modification, using the enzymolysis xylogen of zirconium white modification as sorbent material, and the orthophosphoric acid salt in Adsorption water body and/or fluorion.
The water treatment method of the enzymolysis xylogen of above-mentioned employing zirconium white modification, specifically comprises the steps:
The purification of step 1, enzymolysis xylogen:
It is in the aqueous sodium hydroxide solution of 9.0 ~ 10.0 that enzymolysis xylogen is dissolved into pH according to mass volume ratio 1g:10ml, agitation and filtration, and it is 2.0 ~ 3.0 that filtrate hydrochloric acid soln is adjusted to pH, again filter after stirring, filter cake is washed to neutrality, dries to constant weight, obtains pretreated enzymolysis xylogen;
The preparation of the enzymolysis xylogen of step 2, zirconium white modification:
The pretreated enzymolysis xylogen that step 1 is obtained is dissolved in dimethyl sulfoxide (DMSO), adds 70 wt.% zirconium-n-propylate solution, carries out zirconium reaction, and washing after reaction product cooling, drying, obtain the enzymolysis xylogen of zirconium white modification;
Step 3, adsorption and dephosphorization are except fluorine:
The enzymolysis xylogen of zirconium white modification obtained for step 2 is added in staying water, Adsorption orthophosphoric acid salt and/or fluorion.
In the water treatment method of the enzymolysis xylogen of above-mentioned employing zirconium white modification, in step 1, pH be 9.0 ~ 10.0 aqueous sodium hydroxide solution be employing 20 wt.% sodium hydroxide solution regulate form, described hydrochloric acid soln is the hydrochloric acid soln of 10 wt.%.
In the water treatment method of the enzymolysis xylogen of above-mentioned employing zirconium white modification, in the zirconiumization reaction described in step 2, the mass ratio of enzymolysis xylogen and zirconium-n-propylate is 1:1.5 ~ 6.
In the water treatment method of the enzymolysis xylogen of above-mentioned employing zirconium white modification, the zirconium temperature of reaction described in step 2 is 110 ~ 140 DEG C, and the reaction times is 3 ~ 5 h.
In the water treatment method of the enzymolysis xylogen of above-mentioned employing zirconium white modification, the zirconiumization reaction described in step 2 is carried out in an inert atmosphere.
In the water treatment method of the enzymolysis xylogen of above-mentioned employing zirconium white modification, the reaction product described in step 2 adopts normal hexane, dimethyl sulfoxide (DMSO), dehydrated alcohol and water to wash respectively successively, vacuum-drying under 60 ~ 80 DEG C of conditions after washing.
In the water treatment method of the enzymolysis xylogen of above-mentioned employing zirconium white modification, described water body is 2 ~ 17 P mg/L containing phosphorus concentration, and fluoro-containing concentration is 2 ~ 17 F mg/L.
In the water treatment method of the enzymolysis xylogen of above-mentioned employing zirconium white modification, described adsorption time is 48 ~ 72 h, and adsorption temp is 25 ~ 65 DEG C.
3. beneficial effect
Compared to prior art, the invention has the advantages that:
1, employing hydrothermal method of the present invention also exists the zirconium oxide nano-particle of high dispersing through the enzymolysis xylogen surface of zirconium white modification; Show through adsorption experiment, modified enzymolysis xylogen all has certain adsorption effect to phosphorus and fluorine, and effect increases more to some extent.On adsorption effect, more passing product has and significantly improves, under equal conditions, the adsorptive capacity of phosphorus is significantly better than that wilkinite carries zirconium (8.96 mg/g), pottery carries zirconium (8.49 mg/g) and attapulgite carries the sorbing materials such as zirconium (7.1 mg/g), and the adsorptive capacity of fluorine is significantly better than that silica gel carries zirconium (4.20mg/g), zeolite carries zirconium (4.70 mg/g) and gel carries the sorbing materials such as zirconium (4.10mg/g).
2, conventional art, the mode of load zirconium is mainly with zirconium oxychloride as inorganic zirconium source, and adopt pickling process or coprecipitation method to be prepared from, the sorbing material prepared thus often exists the not high defect of activated adsorption site zirconium utilization ratio; And mainly using zirconium-n-propylate as organic zirconium source in the present invention, after adopting, the method for grafting is prepared from, activated zr exists with Zr-OH form, and can be evenly distributed on material surface, exposes more adsorption site, substantially increases adsorption effect.
3, in addition, when the phosphorus in modified enzymolysis xylogen simultaneously adsorbed water body and fluorine, be effect when being better than independent Phosphate Sorption to the removal effect of phosphorus, fluorine is then contrary.When phosphorus and fluorine adsorb simultaneously, there is competitive adsorption in the activated adsorption site on the modified enzymolysis xylogen surface of zirconium white in phosphorus and fluorine, and is promoter action to the absorption of phosphorus, and be restraining effect to fluorine.In addition, research shows, raised temperature and increase the removal efficiency that ionic strength effectively can improve phosphorus during phosphorus in independent adsorbed water body.
4, the present invention adopt sorbent material in body material enzymolysis xylogen be a kind of biological material, this material is renewable, wide material sources, be preparation biomass energy waste residue, cheap; Through the modified obvious processing effect to phosphorus and fluorine of zirconium white.
5, in addition, the inventive method adsorption treatment mild condition, consuming time short, greatly can improve water treatment efficiency.Therefore, the enzymolysis xylogen of zirconium white modification is applied to the phosphorus in Adsorption water body and fluorine, there is good economy and environment benefit.
Accompanying drawing explanation
Fig. 1 be zirconium white before modified after the full spectrogram of XPS of enzymolysis xylogen.
Fig. 2 be zirconium white before modified after enzymolysis xylogen FTIR figure.
As shown in Fig. 1 in accompanying drawing, modifiedly there is Zr3d and Zr3p peak on enzymolysis xylogen surface, show that the successful load of zirconium white is on enzymolysis xylogen surface.In accompanying drawing Fig. 2 be zirconium white before modified after Fourier's infrared spectrum result of material, as shown in the figure, through the modified enzymolysis xylogen of zirconium white at 1708cm
-1the C=O stretching vibration peak at place disappears, simultaneously at 951cm
-1the new Zr absorption peak of place's appearance one, above result shows, zirconium white by occurring to interact with the oxygen-containing functional group on surface successful load on enzymolysis xylogen.
Embodiment
Describe the present invention below in conjunction with embodiment.Using the enzymolysis xylogen of zirconium white modification as sorbent material in described specific embodiment, carry out Adsorption to the phosphorus in water body and fluorine, absorption adopts static batch processed process.But enforcement the present invention is not limited to the concrete mode described in embodiment, any those skilled in the art, within the scope of the present invention, disclosed technology contents can be utilized to make change or variation, thus obtain the substantially identical embodiment of effect or method.In every case be the aim not departing from technical solution of the present invention, any amendment done described embodiment, equivalent or equivalent change and modification, all still belong in the scope of technical solution of the present invention.Scope of the present invention is not limited with embodiment, and is limited by claim.
embodiment 1
It is 9.0-10.0 that step 1, the sodium hydroxide solution getting 20 wt.% are adjusted to pH, 10.0 g enzymolysis xylogens are dissolved into wherein, filter after abundant stirring, collect filtrate, then to be adjusted to pH with the hydrochloric acid soln of 10 wt.% be 2.0-3.0, again filter after abundant stirring, collect filter cake and it is fully washed to neutrality, at 40 DEG C, vacuum drying is to constant weight, for subsequent use, obtain pretreated enzymolysis xylogen, be denoted as BBL.
Step 2, get 1.0 gBBL and be distributed in 30 ml organic solvent dimethyl sulfoxide (DMSO), be stirred well to after dissolving completely, slowly add the zirconium-n-propylate solution (positive methyl alcohol zirconium quality is 3.17g) of 3 ml 70 wt.% herein, hydro-thermal reaction 3 ~ 5 h is carried out under 110 ~ 140 DEG C of conditions, reaction terminates to filter after naturally cooling, normal hexane, dimethyl sulfoxide (DMSO), dehydrated alcohol and water is adopted fully to wash respectively successively, last vacuum-drying at 60 ~ 80 DEG C, obtain the enzymolysis xylogen of zirconium white modification, be denoted as BBL-Zr.
embodiment 2
With the enzymolysis xylogen BBL-Zr of the zirconium white modification of synthesis in embodiment 1 for sorbent material, adsorption treatment is containing phosphorus water.Concrete adsorption treatment process is as follows: in the EPA bottle of 40 mL tool tetrafluoroethylene pads, carry out Static Adsorption, the quality of sorbent material and phosphate-containing water body is 1:800 ~ 2000 than range of choices, the ratio selected in the present embodiment is 1:2000, pH=6.0 ± 0.2, phosphorus starting point concentration is 14.89 mg/L, not containing NaCl and fluorion in water body, adsorption temp is 25 DEG C, and adsorption time is 24 h.After adsorption equilibrium, the aqueous phase filter through 45 μ L filters, and in filtrate, the concentration of phosphorus adopts molybdenum blue colorimetric method to measure at 700nm place.Recording adsorptive capacity (in phosphorus) is 13.70 mg/g.
embodiment 3
The enzymolysis xylogen preparation method of zirconium white modification is with embodiment 1, and the quality wherein adding positive methyl alcohol zirconium is 1.587 g, and adsorption conditions, with embodiment 2, is finally 4.03 mg/g to the adsorptive capacity of phosphorus.
embodiment 4
The enzymolysis xylogen preparation method of zirconium white modification is with embodiment 1, and the quality wherein adding positive methyl alcohol zirconium is 6.348 g, and adsorption conditions, with embodiment 2, is finally 15.44 mg/g to the adsorptive capacity of phosphorus.
Visible, the quality increasing active ingredient zirconium effectively can improve the removal effect of phosphorus in water body.
embodiment 5
The enzymolysis xylogen preparation method of zirconium white modification is with embodiment 1, and adsorption conditions is with embodiment 2, and wherein adsorption temp is 45 DEG C, and final sorbent material is 15.67 mg/g to the adsorptive capacity of phosphorus.
embodiment 6
The enzymolysis xylogen preparation method of zirconium white modification is with embodiment 1, and adsorption conditions is with embodiment 2, and wherein adsorption temp is 65 DEG C, and final sorbent material is 18.34 mg/g to the adsorptive capacity of phosphorus.
Visible, adsorption temp is 25 ~ 65 DEG C all good removal effect, improves adsorption temp and is conducive to phosphatic Adsorption.
embodiment 7
The enzymolysis xylogen preparation method of zirconium white modification is with embodiment 1, and adsorption conditions, with embodiment 2, containing the NaCl containing 0.1 mol/L in phosphorus water, is 14.35 mg/g to phosphatic Adsorption amount.
embodiment 8
The enzymolysis xylogen preparation method of zirconium white modification is with embodiment 1, and adsorption conditions, with embodiment 2, containing the NaCl containing 1.0 mol/L in phosphorus water, is 20.40 mg/g to phosphatic Adsorption amount.
Visible, the ionic strength improved in water body is conducive to the Adsorption of enzymolysis xylogen to phosphorus of zirconium white modification.
embodiment 9
The enzymolysis xylogen preparation method of zirconium white modification is with embodiment 1, and adsorption conditions is with embodiment 2, and in water body, fluorine starting point concentration is 16.45 mg/L, not containing NaCl and phosphorus in water body, is 9.18 mg/g to the adsorptive capacity of fluorine.
Visible, the enzymolysis xylogen of zirconium white modification has certain removal effect equally to the fluorine in water body.
embodiment 10
The enzymolysis xylogen preparation method of zirconium white modification is with embodiment 1, and adsorption conditions is with embodiment 2, and in water body, phosphorus starting point concentration is 14.19 mg/L, fluorine starting point concentration is 15.84 mg/L, not containing NaCl in water body, be 15.75 mg/g to the adsorptive capacity of phosphorus, 6.64 mg/g are followed successively by the adsorptive capacity of fluorine.
Visible, when phosphorus in water body and fluorine exist simultaneously, create competitive adsorption in the activated adsorption site on the modified enzymolysis xylogen surface of zirconium white, absorption as a result, be promoter action to the absorption of phosphorus, be then restraining effect to fluorine.
Claims (9)
1. adopt a water treatment method for the enzymolysis xylogen of zirconium white modification, it is characterized in that: using the enzymolysis xylogen of zirconium white modification as sorbent material, the orthophosphoric acid salt in Adsorption water body and/or fluorion.
2. the water treatment method of the enzymolysis xylogen of employing zirconium white according to claim 1 modification, is characterized in that specifically comprising the steps:
The purification of step 1, enzymolysis xylogen:
It is in the aqueous sodium hydroxide solution of 9.0 ~ 10.0 that enzymolysis xylogen is dissolved into pH according to mass volume ratio 1g:10ml, agitation and filtration, and it is 2.0 ~ 3.0 that filtrate hydrochloric acid soln is adjusted to pH, again filter after stirring, filter cake is washed to neutrality, dries to constant weight, obtains pretreated enzymolysis xylogen;
The preparation of the enzymolysis xylogen of step 2, zirconium white modification:
The pretreated enzymolysis xylogen that step 1 is obtained is dissolved in dimethyl sulfoxide (DMSO), adds 70 wt.% zirconium-n-propylate solution, carries out zirconium reaction, and washing after reaction product cooling, drying, obtain the enzymolysis xylogen of zirconium white modification;
Step 3, adsorption and dephosphorization are except fluorine:
The enzymolysis xylogen of zirconium white modification obtained for step 2 is added in staying water, Adsorption orthophosphoric acid salt and/or fluorion.
3. the water treatment method of the enzymolysis xylogen of employing zirconium white according to claim 2 modification, it is characterized in that: in step 1, pH be 9.0 ~ 10.0 aqueous sodium hydroxide solution be employing 20 wt.% sodium hydroxide solution regulate form, described hydrochloric acid soln is the hydrochloric acid soln of 10 wt.%.
4. the water treatment method of the enzymolysis xylogen of employing zirconium white according to claim 2 modification, is characterized in that: in the zirconiumization reaction described in step 2, the mass ratio of enzymolysis xylogen and zirconium-n-propylate is 1:1.5 ~ 6.
5. the water treatment method of the enzymolysis xylogen of employing zirconium white according to claim 2 modification, is characterized in that: the zirconium temperature of reaction described in step 2 is 110 ~ 140 DEG C, and the reaction times is 3 ~ 5 h.
6. the water treatment method of the enzymolysis xylogen of employing zirconium white according to claim 2 modification, is characterized in that: the zirconiumization reaction described in step 2 is carried out in an inert atmosphere.
7. the water treatment method of the enzymolysis xylogen of employing zirconium white according to claim 2 modification, it is characterized in that: the reaction product described in step 2 adopts normal hexane, dimethyl sulfoxide (DMSO), dehydrated alcohol and water to wash respectively successively, vacuum-drying under 60 ~ 80 DEG C of conditions after washing.
8. the water treatment method of the enzymolysis xylogen of employing zirconium white according to claim 1 and 2 modification, is characterized in that: described water body is 2 ~ 17 P mg/L containing phosphorus concentration, and fluoro-containing concentration is 2 ~ 17 F mg/L.
9. the water treatment method of the enzymolysis xylogen of employing zirconium white according to claim 1 and 2 modification, is characterized in that: described adsorption time is 48 ~ 72 h, and adsorption temp is 25 ~ 65 DEG C.
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