CN110052249A - A kind of process using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash - Google Patents
A kind of process using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash Download PDFInfo
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- CN110052249A CN110052249A CN201910435351.8A CN201910435351A CN110052249A CN 110052249 A CN110052249 A CN 110052249A CN 201910435351 A CN201910435351 A CN 201910435351A CN 110052249 A CN110052249 A CN 110052249A
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- flyash
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- wastewater treatment
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 56
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title claims abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 15
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000002351 wastewater Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
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- 238000004088 simulation Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
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- 229910007266 Si2O Inorganic materials 0.000 claims description 3
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- 238000006243 chemical reaction Methods 0.000 claims description 3
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- 230000008859 change Effects 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
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- 241000124008 Mammalia Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 239000002956 ash Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
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- 230000036952 cancer formation Effects 0.000 description 1
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- 210000000170 cell membrane Anatomy 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a kind of processes using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash, the method is as follows: (1) is ground up, sieved flyash, dries；It after being cooled to room temperature, is activated in Muffle furnace, the flyash after must activating；(2) it to the flyash acidleach of activation, stood after stirring at normal temperature, filter washing；It after drying, is cooled to room temperature, then finely ground with mortar, obtains acid flyash；(3) acid flyash, chitosan are dissolved in into acetic acid solution, then NaOH is added dropwise, after stirring, filter washing；Finally, drying, being ground up, sieved, Chitosan-coated flyash is obtained；(4) take Chitosan-coated flyash that simulation is added containing Cr (VI) waste water.The present invention combines chitosan with flyash, can reduce cost and improve the absorption property of flyash；In addition, the present invention also strictly optimizes, Chitosan-coated coal ash for manufacturing is standby, each parameter in use process, further increases the absorption property of Chitosan-coated flyash.
Description
Technical field
The present invention relates to technical field of waste water processing more particularly to a kind of handled using Chitosan-coated flyash to contain chromium
The process of waste water.
Background technique
Chromium is one of most common heavy metal, is common in the useless of the industries such as plating, printing, dyeing, mining, metallurgy, the energy
In water.Cr (VI) pollutes the Typical Representative as underground water heavy metal pollution problem by extensive concern.
Chromium is mainly existed in the environment in the form of Cr (III) and Cr (VI).Cr (III) is under alkalinity and neutrallty condition
It is easy on precipitation adsorption to organic and inorganic matter, the mobility very little in water and soil.Cr (III) is that mammal must not
It can lack, participate in and maintain the metabolism of glucose, lipid and protein.Therefore, it is considered that Cr (III) is compared with other pollutions
The concentration of object is lower.Cr (VI) is usually with HCrO4 -And CrO4 2-Form exist in the environment, HCrO4 -And CrO4 2-It is a kind of
The chromate of high dissolution, high toxicity and high fluidity can freely move to the aquatic ecosystem in food chain
In organism, and cross over cell membrane.Accumulation of the Cr (VI) in organism has serious carcinogenesis and a series of harm
The influence of health, such as scytitis and bronchitis.
Recent studies indicate that extraction, biological treatment, absorption, ion exchange/complexing, electrochemical oxidation etc. are a series of
Method can effectively remove Cr in water (VI).Wherein, absorption method is received significant attention because its is at low cost, high-efficient.For chromium
The absorption of ion, common adsorbent have clay mineral, organic polymer, metal onidiges, biomass and flyash.However,
With the continuous intensification of contamination phenomenon, traditional adsorbent is not also able to satisfy public demand increasingly.
Accordingly, it is badly in need of developing a kind of new adsorbent at present, to obtain a kind of utilization adsorbent processing waste water containing chrome
New process.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of utilization Chitosan-coated Chromium-containing Wastewater Treatment by Flyash
Process.
The present invention solves above-mentioned technical problem using following technical scheme:
A kind of process using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash, comprises the following specific steps that:
(1) it by ground 200 mesh of flyash, and is dried for 24 hours in 100 DEG C of thermostatic drying chambers；After being cooled to room temperature,
It places it in Muffle furnace, activates 1h under the conditions of 300 DEG C to get the flyash after activation；
(2) 2mol/L H is chosen2SO4Solution carries out acidleach with flyash of the solid-to-liquid ratio 3g:10mL to activation, and room temperature stirs
It is stood for 24 hours after mixing；After standing, washing is filtered using 0.45 μm of miillpore filter, and after 100 DEG C of thermostatic drying chamber drying, it is cooling
To room temperature；Finally, it is finely ground using mortar, obtain acid flyash；
(3) take 15g acidity flyash, and according to acid flyash: chitosan=15:2 ratio is added to 200 mL 3%
In strength acetic acid solution；It after mixing evenly, is in flocculence in mixed solution and dripping 5%NaOH reagent to solution, and pH=9,
Then 20min is mixed slowly again, after mixing evenly, is washed to neutrality using 0.45 μm of miillpore filter suction filtration；Finally, being set
In 100 DEG C of dryings of thermostatic drying chamber, after dry, is ground, crosses the processing of 200 meshes, obtain Chitosan-coated flyash；
(4) 50g Chitosan-coated flyash is taken, 200mL simulation is added according to ratio of mud 4:1 and contains Cr (VI) waste water,
In, the simulation contains Cr (VI) the concentration 0.05mg/L, pH 5 of Cr (VI) waste water；After mixing, stirred at a temperature of 25 DEG C
90min carries out adsorption reaction.
As one of preferred embodiment of the invention, flyash is derived from the coal-fired electricity in the town Huaibei City Lin Huan in the step (1)
Factory.
As one of preferred embodiment of the invention, ingredient and corresponding content that the flyash includes are as follows: 1.87% MgO,
7.71%Al2O3, 13.06%Si2O, 0.49%K2O, 63.84%CaO, 0.14%Na2O, 3.46% Fe2O3, it is 9.43% micro
Element.
As one of preferred embodiment of the invention, the H2SO4, NaOH, acetic acid reagent be that analysis is pure.
As one of preferred embodiment of the invention, the chitosan is analysis pure chitosan, deacetylation >=96.5%.
The present invention compared with prior art the advantages of be: chitosan and chitosan are often used as adsorbent material；Wherein, shell
Glycan adsorption effect is good, but price is higher；And flyash, it is the solid waste of mass production, quantity is more and cheap；This hair
It is bright to combine chitosan with flyash, enable chitosan that the modified flyash in surface is made as surface modifier, to containing Cr
(VI) waste water is handled, and can both save the usage amount of chitosan, reduces cost, can be also modified flyash to mention
The absorption property of high fly-ash；In addition, the present invention also strictly optimizes, Chitosan-coated coal ash for manufacturing is standby, in use process
Each parameter, the experiment proved that:
(1) as chitosan 2g, acid flyash 15g, acetic acid concentration 3%, adsorption effect is best；
(2) under the conditions of 25 DEG C, pH=5, Cr (VI) concentration 0.05mg/L, when adsorbing 90min, reach theoretical maximum
Adsorbance is 0.5mg/kg, and practical maximal absorptive capacity is 0.48mg/kg.
Detailed description of the invention
Fig. 1 is the adsorbance change curve in embodiment 3 under different pH condition；
Adsorbance when Fig. 2 is difference Cr (VI) concentration in embodiment 3 changes over time curve graph；
Adsorption efficiency when Fig. 3 is difference Cr (VI) concentration in embodiment 3 changes over time curve graph；
Fig. 4 is the metamorphosis figure of flyash in embodiment 4 (in figure, A figure is that before modified, B figure is modified)；
Fig. 5 is the SEM image of flyash in embodiment 4 (in figure, a figure is that before modified, b figure is modified)；
Fig. 6 is the EDS energy spectrum analysis figure of Area 1 in embodiment 4；
Fig. 7 is the EDS energy spectrum analysis figure of Area 2 in embodiment 4；
Fig. 8 is the X ray diffracting spectrum of flyash sample before modified in embodiment 5；
Fig. 9 is the X ray diffracting spectrum of modified flyash sample in embodiment 5.
Specific embodiment
Elaborate below to the embodiment of the present invention, the present embodiment under the premise of the technical scheme of the present invention into
Row is implemented, and the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment 1
A kind of process using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash of the present embodiment, including have as follows
Body step:
(1) it by ground 200 mesh of flyash, and is dried for 24 hours in 100 DEG C of thermostatic drying chambers；After being cooled to room temperature,
It places it in Muffle furnace, activates 1h under the conditions of 300 DEG C to get the flyash after activation.
(2) 2mol/L H is chosen2SO4Solution carries out acidleach with flyash of the solid-to-liquid ratio 3g:10mL to activation, and room temperature stirs
It is stood for 24 hours after mixing；After standing, washing is filtered using 0.45 μm of miillpore filter, and after 100 DEG C of thermostatic drying chamber drying, it is cooling
To room temperature；Finally, it is finely ground using mortar, obtain acid flyash.
(3) take 15g acidity flyash, and according to acid flyash: chitosan=15:2 ratio is added to 200 mL 3%
In strength acetic acid solution；It after mixing evenly, is in flocculence in mixed solution and dripping 5%NaOH reagent to solution, and pH=9,
Then 20min is mixed slowly again, after mixing evenly, is washed to neutrality using 0.45 μm of miillpore filter suction filtration；Finally, being set
In 100 DEG C of dryings of thermostatic drying chamber, after dry, is ground, crosses the processing of 200 meshes, obtain Chitosan-coated flyash.
(4) 50g Chitosan-coated flyash is taken, 200mL simulation is added according to ratio of mud 4:1 and contains Cr (VI) waste water,
In, the simulation contains Cr (VI) the concentration 0.05mg/L, pH 5 of Cr (VI) waste water；After mixing, stirred at a temperature of 25 DEG C
90min carries out adsorption reaction.
Further, flyash is derived from the town Huaibei City Lin Huan coal-burning power plant in step (1), including ingredient and accordingly contain
Amount are as follows: 1.87%MgO, 7.71%Al2O3, 13.06%Si2O, 0.49%K2O, 63.84%CaO, 0.14%Na2O, 3.46%
Fe2O3, 9.43% microelement.
Further, reagent H2SO4, NaOH, acetic acid be analyze pure (Aladdin Industrial Corporation)；
Chitosan (deacetylation >=96.5%) is to analyze pure (Sinopharm Chemical Reagent Co., Ltd.).
Embodiment 2
The present embodiment is to illustrate " the chitosan dosage F in preparation process1", " acid flyash dosage F2", " second
Acid concentration C3" three factors are to " coal ash " the influence of adsorption effect after before modified.
Choose chitosan dosage F1, acid flyash dosage F2, acetic acid concentration C3Three factors, each factor take 3
A level, establishes L9(33) orthogonal design table, the coal ash after comparison before modified obtains flyash to the adsorption effect of Cr (VI)
Modified optimum combination (Orthogonal experiment results are shown in Table 1).Wherein, it is measured and is adsorbed using two hydrazine spectrophotometry of diphenyl phosphinylidyne
Front and back Cr (VI) mass concentration.Adsorption efficiencyρ and ρ0Effects of ion respectively before and after absorption
Mass concentration, unit: mg/L.AdsorbanceV represents liquor capacity, mL；M is modified material quality, g.
1 Orthogonal experiment results of table
As shown in Table 1, the sequence of influence of each factor to adsorbent adsorbance from big to small are as follows: chitosan > acetic acid concentration
> acidity flyash.Also, judging from the experimental results, as chitosan 2g, acetic acid concentration 3%, acidity flyash 15g, absorption
Efficiency highest, optimum combination A2C2B3。
Embodiment 3
The present embodiment is to illustrate " pH value of waste water ", " waste water Cr (VI) concentration " and " absorption during coming into operation
Influence of the time " to " Chitosan-coated flyash " adsorption effect.
There are many factor for influencing absorption, such as adsorption time, adsorbent mass, pollutant concentration and pH value.
1, the influence of pH value of waste water:
It is particularly important to adsorption process to control pH value, because the variation of pH value can change the form of Cr in solution (VI).
As pH > 8.2, CrO4 2-It is stable in the presence of in solution；As 5 < pH < 8.2, Cr (VI) is with Cr2O7 -And HCrO4 -Form exist；
As pH < 8.2, there are H in solution2CrO4.The adsorption capacity and zeta current potential of pH value influence adsorbent.With the increasing of pH value
Add, the protonation of adsorbent reduces, and hinders Anion-adsorption.
Since chromate waste water is generally acid waste water in practical application, modification is tested within the scope of pH 2-10
Material is to the absorption property of Cr (VI), and waste water Cr (VI) concentration is 0.05mg/L, and adsorbent amount 50g, temperature is 25 DEG C,
Adsorption time 90min.
(in figure, abscissa indicates pH value to absorption result, and ordinate indicates adsorbance q as shown in Figure 1t).As shown in Figure 1,
As pH=5, adsorption capacity highest；When pH value is 2-5, adsorbance is gradually increased with the increase of pH value, this may be
H2CrO4The result that concentration gradually decreases；And pH value be 5-10 when, adsorbance is gradually reduced with being continuously increased for pH value.Its
In, in pH=4 and pH=6.5, adsorption capacity is similar；When pH is greater than 6.5, adsorption capacity is reduced rapidly.The result shows that
The present embodiment Chitosan-coated flyash keeps good adsorption capacity within the scope of pH value 1-4.
2, the influence of waste water Cr (VI) concentration:
0.001,0.01, tetra- 0.05,0.1mg/mL Cr (VI) concentration gradients are chosen, and test changes under corresponding condition
Absorption property of the property material to Cr (VI)；Wherein, wastewater pH 5.0, adsorbent amount 50g, temperature are 25 DEG C.
(in Fig. 2, abscissa indicates that adsorption time t, ordinate indicate adsorbance q to absorption result as shown in Figure 2 and Figure 3t；
In Fig. 3, abscissa indicates that adsorption time t, ordinate indicate adsorbance Cr (VI) adsorption efficiency).By Fig. 2, Fig. 3 it is found that with
The adsorption capacity of the increase of pollutant concentration, Chitosan-coated flyash increases, but adsorption efficiency not necessarily increases；Work as pollution
When object concentration is more than 0.05mg/L, since the absorbent concentration used is lower, it is not enough to adsorb extra pollutant, absorption effect
Rate reduces instead.Therefore, in practical applications handle high density pollution water when, need to increase the dosage of adsorbent, with keep compared with
High adsorption efficiency.
3, the influence of adsorption time
Modified material is tested in 0-160min time range to the absorption property of Cr (VI)；Wherein, wastewater pH
5.0, Cr (VI) concentration are 0.001,0.01,0.05 and 0.1mg/mL, and adsorbent amount 50g, temperature is 25 DEG C.
(in Fig. 2, abscissa indicates that adsorption time t, ordinate indicate adsorbance q to absorption result as shown in Figure 2 and Figure 3t；
In Fig. 3, abscissa indicates that adsorption time t, ordinate indicate adsorbance Cr (VI) adsorption efficiency).By Fig. 2, Fig. 3 it is found that with
The increase of adsorption time, the adsorption capacity of Chitosan-coated flyash are integrally in becoming for " first increasing, rear gentle " with adsorption efficiency
Gesture, and when adsorption time reaches 90min, reach peak.
Embodiment 4
Morphology characterization of the present embodiment to illustrate Chitosan-coated flyash of the present invention.
Morphology characterization is detected by cold field emission scanning electron microscope (S-4800) and energy disperse spectroscopy, amplification factor 1K, is added
Fast voltage 2.0kV, operating distance 16.3mm.
The metamorphosis figure of flyash is shown in Fig. 4, and in figure, A figure is that before modified, B figure is modified (chitosan i.e. of the present invention
Coat flyash).Specific surface area and interlamellar spacing all increase after flyash acidleach, and surface is in loose webs structure, meanwhile, shell is poly-
Sugar inherently has cohesion, absorption and sedimentation function, further enhances the ability of Powder ash adsorption Cr (VI).Fig. 4 shows to inhale
Very big change has occurred in attached dose of microscopic appearance, becomes the lesser particulate matter of systematicness, and surface becomes more coarse, increases
Its surface area and porosity are added, so that it be made to improve adsorption capacity to a certain extent.
The SEM image of flyash is specifically shown in Fig. 5 after before modified, and Fig. 5 a is that before modified, selected region is Area 1；Figure
5b is that modified, selected region is Area 2.Fig. 6 is shown in EDS energy spectrum analysis corresponding with Fig. 5 a selection area, selects with Fig. 5 b
Determine the corresponding EDS energy spectrum analysis in region and sees Fig. 7.By under room temperature before modified after flyash different location energy spectrum analysis table is made,
As shown in table 2.
Rear flyash different location energy spectrum analysis comparison before modified under 2 room temperature of table
As can be seen from Table 2, the component of EDS Area1 is significantly more than EDS Area2, EDS Area1 essential element
There are C, O, Fe, Mg, Al, Si, S, Cu, Ca, Ti, Zn etc., but main body is mainly constituted by C, Ca, remaining constituent content is less, and
EDS Area2 mainly by C, Al, Si, the elements such as Ca, Fe form, the constituent contents such as Al, Si, Fe are higher.The shell of crystal structure
Glycan coats flyash and is more conducive to adsorb Cr (VI) in water.
Embodiment 5
XRD, laser particle size analysis of the present embodiment to illustrate Chitosan-coated flyash of the present invention.
Flyash and CWF mineral composition are measured by XRD (Smart Lab) x ray diffractometer x, emitter material Cu
Target, generator tube pressure are 40kV, tube current 100mA, scanning range from 10-90 ° of 2 θ, with 0.01 ° of speed to sample into
Row continuous scanning, before modified after sample XRD spectrum see Fig. 8, Fig. 9 (Fig. 8 be before modified, Fig. 9 be it is modified, in figure, Qua table
Show that quartz, Sea indicate that seamanite, But indicate that buttgenbachite, Ger indicate gerhardtite).
Minerals in flyash are the preservation carriers of microelement, and the stability of minerals and its lattice energy cease manner of breathing
It closes, lattice energy is higher, and the stability of mineral is better.Modified material Minerals are based on Qua (quartz), as shown in Table 3, silicic acid
Saline minerals lattice energy is relatively high, and modified material structure is relatively stable.
3 part minerals lattice energy (kJmol of table-1)
| SiO2 | FeS2 | CuFeS2 | ZnS | CaCO3 |
| 6280 | 3506 | 3498 | 3235 | 2711 |
Chitosan molecule contains more amino, when it is dissolved in acid solution, that is, has positive charge, can be with crystalline substance
The molecule of external surface is bound to each other to form covalent bond.Since the chitosan molecule chain with positive charge is very long, hardly possible insertion fine coal
Between the hole of grey crystal, flyash-chitosan complexes are only formed.By Fig. 8, Fig. 9 it is found that before Chitosan-coated flyash
The position of diffraction maximum illustrates that modified flyash crystal structure types do not change there is no variation afterwards.Therefore, may be used
The mechanism of modification for deducing fly ash loading chitosan is the chemical bonding effect of flyash and positively charged chitosan.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (5)
1. a kind of process using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash, which is characterized in that including following specific
Step:
(1) it by ground 200 mesh of flyash, and is dried for 24 hours in 100 DEG C of thermostatic drying chambers；After being cooled to room temperature, set
In Muffle furnace, 1h is activated under the conditions of 300 DEG C to get the flyash after activation；
(2) 2mol/L H is chosen2SO4Solution carries out acidleach to the flyash of activation with solid-to-liquid ratio 3g:10mL, quiet after stirring at normal temperature
It sets for 24 hours；After standing, washing is filtered using 0.45 μm of miillpore filter, and after 100 DEG C of thermostatic drying chamber drying, be cooled to room temperature；
Finally, it is finely ground using mortar, obtain acid flyash；
(3) take 15g acidity flyash, and according to acid flyash: chitosan=15:2 ratio is added to 200mL3% concentration second
In acid solution；It after mixing evenly, is in flocculence in mixed solution and dripping 5%NaOH reagent to solution, and pH=9, then again
20min is mixed slowly, after mixing evenly, is washed to neutrality using 0.45 μm of miillpore filter suction filtration；Finally, it is dry to place it in constant temperature
The 100 DEG C of dryings of dry case after dry, are ground, cross the processing of 200 meshes, obtain Chitosan-coated flyash；
(4) 50g Chitosan-coated flyash is taken, 200mL simulation is added according to ratio of mud 4:1 and contains Cr (VI) waste water, wherein is described
Simulation contains Cr (VI) the concentration 0.05mg/L, pH5 of Cr (VI) waste water；After mixing, 90min is stirred at a temperature of 25 DEG C and is adsorbed
Reaction.
2. the process according to claim 1 using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash, feature exist
In flyash is derived from the town Huaibei City Lin Huan coal-burning power plant in the step (1).
3. the process according to claim 2 using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash, feature exist
In the ingredient and corresponding content that the flyash includes are as follows: 1.87%MgO, 7.71%Al2O3, 13.06%Si2O, 0.49%
K2O, 63.84%CaO, 0.14%Na2O, 3.46%Fe2O3, 9.43% microelement.
4. the process according to claim 1 to 3 using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash,
It is characterized in that, the H2SO4, NaOH, acetic acid reagent be that analysis is pure.
5. the process according to claim 1 to 3 using Chitosan-coated Chromium-containing Wastewater Treatment by Flyash,
It is characterized in that, the chitosan is analysis pure chitosan, deacetylation >=96.5%.
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