CN104815613A - Preparation method and applications of lanthanum-loaded biochar arsenic-removing adsorbent - Google Patents
Preparation method and applications of lanthanum-loaded biochar arsenic-removing adsorbent Download PDFInfo
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- CN104815613A CN104815613A CN201510162016.7A CN201510162016A CN104815613A CN 104815613 A CN104815613 A CN 104815613A CN 201510162016 A CN201510162016 A CN 201510162016A CN 104815613 A CN104815613 A CN 104815613A
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Abstract
The present invention discloses a preparation method and applications of a lanthanum-loaded biochar arsenic-removing adsorbent. The preparation method mainly comprises: washing corn stalks, remove impurities, carrying out air-drying, crushing, screening, carrying out stirring mixing on the corn stalk powder and a lanthanum chloride solution under a certain condition, adjusting the pH value to the alkaline state, removing excess chlorine ions from the solution, and carrying out anoxybiotic calcination on the mixture for a certain time at a certain temperature so as to prepare the nanometer lanthanum oxide-loaded biochar material. According to the present invention, the prepared lanthanum-loaded biochar can be used for treating pentavalent arsenic ions in wastewater, and has characteristics of simple preparation, low cost, high adsorption efficiency, good application prospect, and the like.
Description
Technical field
The present invention relates to preparation method and the application thereof of a kind of year lanthanum charcoal arsenic-removing adsorption agent, can be applicable to arsenic pollutant effluents adsorption treatment, belong to wastewater treatment and agricultural resources utilizes association area.
Background technology
In recent years, Heavy Metals in Waters pollutes day by day serious, and arsenic is wherein one of most important heavy metal pollution of water body thing.Directly discharge can destroy water ecological setting containing arsenic sewage, also can be detrimental to health, Long Term Contact arsenic can cause the cancer such as cutaneum carcinoma, lung cancer.The World Health Organization specifies: the Cmax of Arsenic in Drinking Water is 0.01mg/L.Therefore, the focus that the concentration reducing arsenic in water body is research always and pays close attention to.Existing arsenic removal technology mainly comprises electricity flocculation, chemical precipitation, filtration, counter-infiltration, ion-exchange, film process etc., and wherein, absorption method, as a kind of method of novel hot topic, receives and pays close attention to widely.Absorption method mainly utilizes the Van der Waals force of sorbing material, the physics chemical action such as ion-exchange, and absorption exchanges arsenic ion, has easy operation, selective various, with low cost, the advantage such as can to reuse.
In absorption method, comparatively conventional is physisorphtion, and its principle is the pollutant utilizing the porosity characteristic of some material surface to come in adsorbed water body, and such as active carbon, charcoal are exactly this polyporous materials.Wherein, charcoal developed a class new material rapidly in recent years, utilize stalk material anoxic or anoxybiotic, lower than 700 DEG C of conditions under pyrolysis produce, there is macroporosity and specific area, have good stability, distribution of pores is flourishing, more can carbon fixation and emission reduction after being manured into soil, obtain in recent years continuing and studying widely, administer for the treatment of water pollution as a kind of sorbing material.But charcoal surface band negative electricity, polluter (arsenic ion in the such as arsenate) adsorption capacity existed anionic form is poor, need improve its adsorption capacity by surperficial or structurally-modified.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide the preparation method of a kind of year lanthanum charcoal arsenic-removing adsorption agent, achieve the minimizing of waste straw recycling and lanthanum consumption, reduce production cost, very good to the pentavalent arsenic ionic adsorption effect in waste water.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
A preparation method for year lanthanum charcoal arsenic-removing adsorption agent, comprises the steps:
S1, maize straw cleaned and removes impurity, air-dry rear fragmentation, crossing 2mm sieve, stand-by;
S2, the maize straw powder obtained by step S1 and lanthanum chloride solution are by 10g:(100-200) amount ratio of mL stirs and evenly mixs, and wherein in lanthanum chloride solution, the quality of La element and the mass ratio of maize straw powder are 5%-15%; Then in above-mentioned mixed liquor, dropwise add NaOH solution while stirring, regulate pH to 8 ~ 12 of mixed liquor, continue stirring 30 ~ 300min, then carry out centrifugation, outwell supernatant, by residual settlement thing with 95% ethanol wash to leacheate without Cl
-, the product after cleaning is dried to constant weight;
S3, the product obtained by step S2 are placed in the roasting of Muffle furnace anoxybiotic, design temperature 200 ~ 600 DEG C is warming up to the heating rate of 10-20 DEG C/min, and keep 10 ~ 100min at this temperature, be cooled to room temperature again, then take out carbonizing production, using deionized water repeatedly to clean to leacheate is neutrality, dries, finally cross 0.25mm sieve, carry lanthanum charcoal.
Preferably, in step S2, the amount ratio of maize straw powder, lanthanum chloride solution is 10g:(100-150) mL, wherein in lanthanum chloride solution, the quality of La element and the mass ratio of maize straw powder are 8%-15%; The pH regulating mixed liquor is 10, and mixing time is 60min.
More preferably, in step S2, centrifugal rotational speed is 2000 ~ 5000rpm, and centrifugation time is 2 ~ 10min.
Further preferably, in step S2, utilize the AgNO of 0.1M
3solution detects in leacheate whether there is Cl
-.
As a preferred embodiment, in step s 2, w (La)/w (stalk)=9.47%; In step S3, design temperature is 300 DEG C, and the retention time is 20min.
The lanthanum-carried charcoal that preceding method prepares, dropped in the waste water containing pentavalent arsenic ion, adsorption effect is good, and applied environment is acid.
We describe charcoal in the introduction and there is good characterization of adsorption, but not good to the adsorption capacity of anion, and applicant make use of the compound zero-potential point comparatively high of lanthanum and lanthanum, is applied to the absorption arsenic removal research of water body.But the general existence form of the compound of lanthanum and lanthanum is the Powdered of ultra-fine grain, directly drops in water body and use, easily produce secondary pollution; Meanwhile, fine particle is stacked into and produces larger resistance to mass tranfer together, hinders arsenic ion to enter into accumulation body inside, reduces removal efficiency, increase use cost.The present invention then make use of the porosity characteristic of charcoal, in conjunction with the unique advantage of compound in absorption arsenic removal of lanthanum and lanthanum, the synergy of both performances, the nano particle of lanthanum is loaded to the surface of charcoal, prepare a kind of year lanthanum charcoal, can realize reducing costs, improve mass-transfer performance, and then reach targets such as promoting adsorption efficiency.
Usefulness of the present invention is: (1) provided by the invention year lanthanum charcoal preparation method is easy and simple to handle, and success rate is high, with low cost, and raw material is easy to get, and is easy to industrialization and goes into operation; (2) method Appropriate application provided by the invention straw refuse, decrease the environmental pollution that crop straw burning causes, the recycling for agriculture and forestry organic waste material further provides new approaches; (3) what method provided by the invention obtained carries lanthanum charcoal, and arsenic-adsorbing ion successful, can be applicable to technical field of waste water processing.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph carrying lanthanum charcoal that embodiments of the invention 1 prepare;
Fig. 2 is the XRF diffraction analysis results carrying lanthanum charcoal that embodiments of the invention 1 prepare;
Fig. 3 is that the fourier infrared carrying lanthanum charcoal that embodiments of the invention 2 prepare detects collection of illustrative plates;
Fig. 4 is the x-ray photoelectron spectroscopy spectrogram carrying lanthanum charcoal that embodiments of the invention 3 prepare; Wherein, scheming (a) is score; Figure (b) is C1s swarming spectrogram; Figure (c) is O1s swarming spectrogram; Figure (d) is La3d swarming spectrogram;
Fig. 5 is the dynamic absorption curve of embodiments of the invention 4;
Fig. 6 is the dynamic absorption matched curve of embodiments of the invention 4; Wherein scheme (a) and adopt pseudo-first-order kinetic model; Figure (b) adopts pseudo-second order kinetic model;
Fig. 7 carries lanthanum charcoal dosage to affect result to the clearance of As (V) in embodiments of the invention 5;
Fig. 8 is that in embodiments of the invention 6, pH affects result to the clearance of As (V);
Fig. 9 is F in embodiments of the invention 6
-, Cl
-, CO
3 2-and concentration affects result to the clearance of As (V);
Figure 10 is reciprocation response surface design between the Different Effects factor in embodiments of the invention 7; Wherein scheming (a) is w (La)/w (stalk) and pyrolysis temperature; Figure (b) is the time of staying and pyrolysis temperature; Figure (c) is w (La)/w (stalk) and the time of staying;
Figure 11 is the langmuir models fitting curve of the adsorption isotherm data in embodiment 5.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, concrete introduction is done to the present invention.Wherein, described method is conventional method if no special instructions; Described raw material all can obtain from open commercial sources if no special instructions.
Embodiment 1
Be raw material with maize straw, clean and remove impurity, air-dry rear fragmentation, cross 2mm sieve.Getting the maize straw powder that 10g sieves joins in the 100mL solution containing 1.2g seventy flavors pearl pill, and in above-mentioned mixed solution, dropwise adding NaOH solution while stirring to the pH of mixed liquor is 8, continues to stir 30min.By stirring, the product obtained is centrifugal, and centrifugal rotational speed is 2000rpm, and centrifugation time is 2min, outwells supernatant after centrifugal end, and residual settlement thing solid be can't detect Cl with in 95% ethanol purge to leacheate
-(adopt 0.1MAgNO
3detect).Solid after cleaned is dried to constant weight, be placed in the roasting of Muffle furnace anoxybiotic, 200 DEG C are warming up to the heating rate of 20 DEG C/min, and 10min is kept under this temperature conditions, to be cooledly to room temperature, take out carbonizing production, the pH using deionized water repeatedly to clean to leacheate is neutrality, dries, cross 0.25mm sieve, target product can be obtained and carry lanthanum charcoal (La-biochar).
Embodiment 2
Be raw material with maize straw, clean and remove impurity, air-dry rear fragmentation, cross 2mm sieve.Getting the maize straw that 10g sieves joins in the 100mL solution containing 2.06g seventy flavors pearl pill, and in above-mentioned mixed solution, dropwise add NaOH solution is while stirring 10 to pH, continues to stir 60min.By stirring, the product obtained is centrifugal, and centrifugal rotational speed is 3500rpm, and centrifugation time is 5min, outwells supernatant after centrifugal end, and residual settlement thing solid be can't detect Cl with in 95% ethanol purge to leacheate
-(adopt 0.1M AgNO
3detect).Solid after cleaned is dried to constant weight, be placed in the roasting of Muffle furnace anoxybiotic, 300 DEG C are warming up to the heating rate of 20 DEG C/min, and 20min is kept under this temperature conditions, to be cooledly to room temperature, take out carbonizing production, the pH using deionized water repeatedly to clean to leacheate is neutrality, dries, cross 0.25mm sieve, target product can be obtained and carry lanthanum charcoal (La-biochar).
Embodiment 3
Be raw material with maize straw, clean and remove impurity, air-dry rear fragmentation, cross 2mm sieve.Getting the maize straw that 10g sieves joins in the 100mL solution containing 3g seventy flavors pearl pill, and in above-mentioned mixed solution, dropwise add NaOH solution is while stirring 12 to pH, continues to stir 300min.By stirring, the product obtained is centrifugal, and centrifugal rotational speed is 5000rpm, and centrifugation time is 10min, outwells supernatant after centrifugal end, and residual settlement thing solid be can't detect Cl with in 95% ethanol purge to leacheate
-(adopt 0.1M AgNO
3detect).Solid after cleaned is dried to constant weight, be placed in the roasting of Muffle furnace anoxybiotic, 600 DEG C are warming up to the heating rate of 20 DEG C/min, and 100min is kept under this temperature conditions, to be cooledly to room temperature, take out carbonizing production, the pH using deionized water repeatedly to clean to leacheate is neutrality, dry, cross 0.25mm sieve, target product can be obtained and carry lanthanum charcoal (La-biochar)
Morphology analysis and Characterization of The Products
(1), Analysis of Surface Topography is carried out with the lanthanum charcoal that carries that ESEM is obtained to embodiment 1.
Fig. 1 is the SEM figure of the product of embodiment 1, and as shown in Figure 1, there is more fold on the charcoal surface prepared by method of the present invention, and has granular object, analyzes the nano particle that it may be lanthanum.
Calculate through Measurement and analysis, the specific area obtaining lanthanum-carried front and back charcoal is 27.98m respectively
2/ g and 128.95m
2/ g, pore volume is respectively 0.05cc/g and 8.04cc/g, and pore diameter is respectively 3.88nm and 4.3nm.That is: the charcoal specific area after load is 4.6 times before load, and the pore volume of the charcoal after load and pore diameter are respectively 161 times and 1.1 times before load, and this is just for biological carbon surface provides more adsorption site.
(2), carry out Elemental Composition with year lanthanum charcoal that XRF diffraction analysis instrument is obtained to embodiment 1 to analyse.
As shown in Figure 2, in the product of embodiment, except carbon, oxygen, nitrogen, hydrogen four kinds of basic elements, lanthanum element is maximum carrying percentage shared in lanthanum charcoal.Can obtain thus, through preparing a large amount of lanthanum element of the charcoal successful load in surface.
(3), configuration of surface analysis is carried out with the lanthanum charcoal that carries that fourier infrared spectrophotometer is obtained to embodiment 2.
As Fig. 3, at 3200 ~ 3600cm
-1there is powerful broad absorption band in place, this absorption band comes from the vibration of hydroxyl, and the deformation vibration of-COOH is positioned at 1500cm
-1place.After serial reaction, this products therefrom is at low frequency region 850-1000cm
-1having occurred obvious absorption band, is because the lattice vibration mode of La-O and La-OH, lanthanum is described by successful load on charcoal surface.
(4), elementary analysis is carried out with the lanthanum charcoal that carries that x-ray photoelectron spectroscopy is obtained to embodiment 3.
Be made up of two peaks the C1s spectrum of Fig. 4 (b), La-biochar, Na
2cO
3(peak 1,289.4eV) and C (peak 2,284.8eV), wherein, the main composition that peak 2 describes this material is carbon, and the appearance at peak 1 is because employ NaOH solution in material preparation process to regulate pH, introduces sodium element.
As follows from Fig. 4 (c), O1s spectral composition: Na
2cO
3(peak 3,533.2eV), La
2o
3(peak 4,532.8eV) and La
2(C
2o
4)
3(peak 5,531.5eV).From Fig. 4 (d), La3d spectrum by La
2o
3(peak 6,835.3eV) and La
2(C
2o
4)
3(peak 7,838.8eV) forms.O1s spectrum and La3d spectrum all show La element by successful load on the surface of La-biochar, and the main existence form of lanthanum element is La
2o
3and La
2(C
2o
4)
3.
Embodiment 4
The present embodiment is the application examples of carrying lanthanum charcoal absorption pentavalent arsenic ion: dynamic absorption.
Get year lanthanum charcoal that 1g embodiment 1 prepares gained, dropping into containing As (V) concentration is 50mgL
-1waste water in, as shown in Figure 5, through 60min, absorption substantially reach balance, adsorption efficiency reaches 89.74%.
Pseudo-first-order and pseudo-second order kinetic model is adopted to carry out matching to the dynamic process that La-biochar adsorbs As (V).As shown in Figure 6, pseudo-first-order dynamics of comparing coefficient correlation (R
2=0.6398), the coefficient correlation (R of accurate second motive force
2=0.9284) closer to 1.000, describe pseudo-second order kinetic model and be more suitable for describing La-biochar to the absorption of As (V), and the application of lanthanum charcoal in pentavalent arsenic ionic soil waste water in this year is feasible.
Embodiment 5
The present embodiment is the application examples of carrying lanthanum charcoal absorption pentavalent arsenic ion: isothermal adsorption.
The lanthanum charcoal that carries getting 0.025g, 0.05g, 0.075g, 0.1g and 0.2g embodiment 3 respectively obtained joins 50mL containing 50mgL
-1as (V) waste water in, be placed in water-bath constant temperature oscillator and shake 24h, rotating speed is 200rpm, keep temperature be 25 DEG C.
Carry lanthanum charcoal dosage to the clearance of As (V) as shown in Figure 7, as expection, As (V) clearance increases along with the increase of adsorbent dosage, tends to balance when adsorbent dosage reaches 2.0g/L.Further, when adsorbent dosage reaches capacity time, As (V) concentration after absorption in solution, lower than 10g/L, can meet the standard restriction of Arsenic in Drinking Water acid ion.
Respectively get 0.05g carry lanthanum charcoal join 50mL respectively containing 10mg/L, 50mg/L, 75mg/L, 100mg/L, 125mg/L As (V) solution in, 25 DEG C in constant temperature oscillator 200rpm vibrate 24h.The isothermal adsorption process that application Freundlich and Langmuir adsorption isotherm line model is used to adsorb La-biochar As (V) carries out matching, Figure 11 is fitting result, found that, the adsorption process of La-biochar to As (V) is more suitable for describing with Langmuir Tellurium determination, illustrate that it is adsorbed as monolayer adsorption to As (V), and maximum adsorption capacity is 38.02mg/g.
Embodiment 6
The present embodiment is the application examples of carrying lanthanum charcoal absorption pentavalent arsenic ion: ambient influnence.
Getting the obtained lanthanum charcoal that carries of 0.05g embodiment 2, to join 50mL containing As (V) concentration be in the solution of 50mg/L, with 0.1M NaOH or HCl, the pH of solution is adjusted to different value, be placed in water-bath constant temperature oscillator and shake 24h, rotating speed is 200rpm, keeps temperature to be 25 DEG C.As shown in Figure 8, La-biochar is to float larger along with the change of pH has of the clearance of As (V).Along with the increase of pH, the adsorption capacity of As (V) is reduced.On the whole, under acid condition, the clearance of La-biochar to As (V) will be significantly higher than alkali condition, illustrates that this year lanthanum charcoal is more suitable in acid condition for removing pentavalent arsenic ionic soil in waste water.
Na is added in distilled water
2hAsO
4, preparation AsO
4 3-concentration is the standard liquid of 50mg/L, then gets 9 parts of standard liquids, adds NaF, NaCl, Na respectively wherein
2cO
3, the F of preparation containing 0.01M, 0.05M, 0.1M tri-concentration scales
-, Cl
-, CO
3 2-mixed solution.Then, respectively get 0.05g La-biochar and join in the above-mentioned each solution of 50mL, As (V) standard liquid simultaneously getting 50mg/L in contrast, is placed in water-bath constant temperature oscillator and shakes 24h, and hunting speed is 200rpm, keeps temperature to be 25 DEG C.Testing result as shown in Figure 9, can be found out, carrying lanthanum charcoal, to remove As (V) substantially unaffected under low concentration anion condition, by negative effect under slightly high concentration carbon acid ion condition.
Embodiment 7
The present embodiment is the optimized fabrication carrying lanthanum charcoal absorption pentavalent arsenic: the utilization of response surface model.High spot reviews key parameter, on the impact of its arsenic-adsorbing acid group, comprises the impact of material ratio, the impact of sintering temperature, the impact of the time of staying.For this reason, the present embodiment uses response surface model to carry out verifying and investigating.
(1), response phase method research optimized fabrication condition
The main affecting factors of preparation La-biochar comprises material ratio w (La)/w (stalk), pyrolysis temperature and the time of staying.According to single factor test pilot study, determine the proper range of each factor optimum level, adopt Box-Behnken model to carry out experimental design.Experimental design factor and level are in table 1.For simplicity, especially because setting up the needs of equation, implication representated by the code names such as A, B, the C related to being discussed hereinafter and listing in the table.
Table 1 response surface design factor and level
According to this experimental design, carry out carrying firing of lanthanum charcoal under different material ratios, pyrolysis temperature, residence-time conditions, then carry to what produce the adsorption test that lanthanum charcoal carries out pentavalent arsenic, obtain its eliminating rate of absorption to pentavalent arsenic, and then the functional relation with aforementioned three key parameters can be set up based on pentavalent arsenic clearance.
(2), response surface experimental result and analysis
Lanthanum charcoal is carried to pentavalent arsenic (AsO according to what fire under different condition prepared by Box-Behnken experimental design
4 3-) eliminating rate of absorption as shown in table 2.
| Run | W (La)/w (stalk) (%) | The time of staying (min) | Pyrolysis temperature (DEG C) | AsO 4 3-Clearance (%) |
| 1 | 5.00 | 100 | 450 | 4.70 |
| 2 | 10.00 | 60 | 450 | 68.36 |
| 3 | 10.00 | 60 | 450 | 67.71 |
| 4 | 10.00 | 100 | 300 | 44.89 |
| 5 | 10.00 | 60 | 450 | 68.43 |
| 6 | 10.00 | 20 | 600 | 28.28 |
| 7 | 5.00 | 20 | 450 | 9.76 |
| 8 | 5.00 | 60 | 600 | 45.81 |
| 9 | 10.00 | 60 | 450 | 67.79 |
| 10 | 10.00 | 20 | 300 | 94.54 |
| 11 | 15.00 | 100 | 450 | 22.56 |
| 12 | 10.00 | 100 | 600 | 53.76 |
| 13 | 15.00 | 60 | 300 | 98.14 |
| 14 | 15.00 | 20 | 450 | 38.37 |
| 15 | 5.00 | 60 | 300 | 23.94 |
| 16 | 10.00 | 60 | 450 | 68.39 |
| 17 | 15.00 | 60 | 600 | 17.35 |
Table 2Box – Behnken experimental design and corresponding Arsenate adsorption clearance
Adopt Box-Behnken model to carry out the multinomial matching of secondary to the result that Three factors-levels is tested, the relation between eliminating rate of absorption and Three factors can be set up:
Y％＝68.14-2.69AB-25.67AC
+11.53A-5.63B-14.54C
+18.78A
2-20.12B
2+7.35C
2
The variance analysis of model in table 3, the entire variable quadratic regression equation coefficients R of institute's matching
2be 0.9998, show the good relationship between predicted value and measured value, this regression equation can be utilized preferably to determine best removal technique.
| Source | Quadratic sum | The free degree | All square | F value | P value |
| Model | 12734.81 | 9 | 1414.98 | 4456.03 | < 0.0001 is remarkable |
| A | 1062.84 | 1 | 1062.84 | 3347.07 | ＜0.0001 |
| B | 253.58 | 1 | 253.58 | 798.56 | ＜0.0001 |
| C | 1691.00 | 1 | 1691.00 | 5325.28 | ＜0.0001 |
| AB | 28.89 | 1 | 28.89 | 90.98 | ＜0.0001 |
| AC | 2634.77 | 1 | 2634.77 | 8297.38 | ＜0.0001 |
| BC | 1411.13 | 1 | 1411.13 | 4443.91 | ＜0.0001 |
| A2 | 3583.43 | 1 | 3583.43 | 11284.89 | ＜0.0001 |
| B2 | 1703.72 | 1 | 1703.72 | 5365.33 | ＜0.0001 |
| C2 | 227.28 | 1 | 227.28 | 715.74 | ＜0.0001 |
| Residual error | 2.22 | 7 | 0.32 | ||
| Lose and intend item | 1.72 | 3 | 0.57 | 4.57 | 0.0882 is not remarkable |
| Error term | 0.50 | 4 | 0.13 | ||
| Summation | 12737.03 | 16 |
The coefficient significance test of table 3 regression equation and variance analysis
As shown in Table 3, significant difference (the P < 0.001 of model) between this experiment selected model different disposal, when the relation that regression equation describes between each factor and response is described, relation between its dependent variable and all independents variable is significant, and namely this experimental technique is reliable.According to polynary quadratic regression equation, AB and AC item interaction factor is negative value, and this illustrates that between w (La)/w (stalk) and the time of staying, pyrolysis temperature be antagonism; The large I of each absolute coefficient judges that the impact order of 3 factors on arsenate clearance is: pyrolysis temperature > w (La)/w (stalk) > time of staying.As shown in Table 3, for the significance test of the regression coefficient in model, the single factor test effect of A, B, C, and reciprocation between them or its curved surface effect (A2, B2, C2) are all significant.
(3), factor interactive analysis
Figure 10 shows, and the reciprocation between AC is better than AB and BC, and the reciprocation between BC is better than AB, and this point can be weighed by the order of magnitude of reciprocation term coefficient.
As shown in Figure 10 (a), when w (La)/w (stalk) is less, raised temperature is larger to the effect improving arsenate clearance, when w (La)/w (stalk) is 5%, when temperature is brought up to 600 DEG C from 300 DEG C, arsenate clearance is only made to improve 22.25%.But, along with the increase gradually of w (La)/w (stalk), improve temperature more and more less for the effect of the clearance of arsenate to La-biochar; When w (La)/w (stalk) is 7.18%, at 300 DEG C and 600 DEG C, arsenate clearance is equal; As w (La)/w (stalk) > 7.18%, the clearance of La-biochar to arsenate generated at 300 DEG C is higher than the clearance at 600 DEG C; And along with the rising gradually of w (La)/w (stalk), at the clearance at 300 DEG C and 600 DEG C, the gap of arsenate clearance is increasing; When w (La)/w (stalk) is 15%, at 300 DEG C preparation La-biochar arsenate clearance than 600 DEG C at prepare La-biochar high by 80.40%, this illustrates when w (La)/w (stalk) is higher, and preparation temperature lower may being more conducive to improves La-biochar to the clearance of arsenate.
Can see clearly from response surface, temperature is lower, and response almost straight line rises, and when temperature is higher, response is without larger change.Inferred by the reciprocation relation of both w (La)/w (stalk) and pyrolysis temperature, maximum arsenate clearance should obtain under the condition of lower temperature and higher w (La)/w (stalk).
As shown in Figure 10 (b), when the time of staying is shorter, not only raising temperature can not make lanthanum charcoal raise the clearance of arsenate, can reduce arsenate clearance on the contrary.When the time of staying is 20min, when temperature is brought up to 600 DEG C from 300 DEG C, arsenate clearance reduces amplitude and reaches 66.64%.Along with the prolongation of the time of staying, the impact of raised temperature on arsenate clearance is more and more less, and when the time of staying is 100min, the La-biochar arsenate clearance generated at 600 DEG C than 300 DEG C at exceeded 8.49%.Inferred by the reciprocation relation of the time of staying and pyrolysis temperature both, maximum arsenate clearance should obtain under lower pyrolysis temperature and the condition of the shorter time of staying.
As shown in Figure 10 (c), similar to the reciprocation of pyrolysis temperature to the time of staying, when w (La)/w (stalk) is less, the prolongation time of staying also can reduce the clearance of La-biochar to arsenate, when w (La)/w (stalk) is 5%, when 20min extends to 100min, arsenate clearance is made to reduce 5.89% the time of staying; But, along with the increase gradually of w (La)/w (stalk), time expand, the reduction amplitude to arsenate clearance was increasing, when w (La)/w (stalk) is 15%, when the time of staying is extended to 100min from 20min, arsenate clearance reduces by 16.64%.This illustrates when w (La)/w (stalk) is higher, and the time of staying shorter may being more conducive to improves La-biochar to the removal of arsenate.Therefore can infer, maximum arsenate clearance should obtain under the condition of the lower time of staying and higher w (La)/w (stalk).
(4), the determination of optimized fabrication condition
The optimization of preparation condition is a relative concept, optimize preparation condition out and preparation target about: merely with realize maximum adsorption ability for objective optimization result out with consider preparation cost simultaneously and comprise economy, time cost etc., optimum results of its generation can be different.The present invention is main criterion (weights of importance is set as peak 5) to carry the maximum adsorption ability of lanthanum charcoal to pentavalent arsenic, be inclined to use lower material ratio (weight setting is medium value 3), the less time of staying (weight setting is 3) and lower temperature (weight setting is 3) simultaneously, use response surface model can obtain having the preparation parameter of the more excellent La-biochar except arsenate efficiency, these parameters are respectively: material ratio w (La)/w (stalk)=9.47%, the time of staying=20min, pyrolysis temperature=300 DEG C.The arsenate maximum material removal rate prepared under this condition is 89.74%, this condition is to obtain La-biochar to the maximum adsorption ability of arsenate for guiding, taken into account preparation cost (be presented as the time of staying and maximum temperature lower, lanthanum consumes less), the optimized fabrication condition obtained achieves the optimum of material property and cost of manufacture.
It is pointed out that the design parameter of this optimized fabrication condition is relevant with the weight of each preparation condition, the optimal conditions adjusting respective weight generation there will be difference.The weight of preparation condition of the present invention is arranged, divide into secondary in essence, also can think that the target of this research is divided into two-stage according to importance: first order target is that the material of preparation will reach the highest to the adsorption capacity of arsenate, therefore weight setting is peak 5, and this is relevant with main purpose of the present invention; Second level index is that preparation condition is minimum, and namely cost is minimum, is divided into again three objectives here: material ratio is minimum, the highest pyrolysis temperature is minimum, the time of staying is the shortest, is 3 in the weight of this setting three sub-goals.With the optimal conditions that this two-stage target obtains, while main consideration absorption property, with reference to preparation cost, there is actual meaning.
To sum up, the preparation method of of the present invention year lanthanum charcoal is simple and easy to realize, and preparation condition is gentle, with low cost and adsorption efficiency is high, can be used for pentavalent arsenic ion in process waste water body, has good application prospect.
More than show and describe general principle of the present invention, principal character and advantage.The technical staff of the industry should understand, and above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops in protection scope of the present invention.
Claims (7)
1. carry a preparation method for lanthanum charcoal arsenic-removing adsorption agent, it is characterized in that, comprise the steps:
S1, maize straw cleaned and removes impurity, air-dry rear fragmentation, crossing 2mm sieve, stand-by;
S2, the maize straw powder obtained by step S1 and lanthanum chloride solution are by 10g:(100-200) amount ratio of mL stirs and evenly mixs, and in described lanthanum chloride solution, the quality of La element and the mass ratio of maize straw powder are 5%-15%; Then in above-mentioned mixed liquor, dropwise add NaOH solution while stirring, regulate pH to 8 ~ 12 of mixed liquor, continue stirring 30 ~ 300min, then carry out centrifugation, outwell supernatant, by residual settlement thing with 95% ethanol wash to leacheate without Cl
-, the product after cleaning is dried to constant weight;
S3, the product obtained by step S2 are placed in the roasting of Muffle furnace anoxybiotic, design temperature 200 ~ 600 DEG C is warming up to the heating rate of 10-20 DEG C/min, and keep 10 ~ 100min at this temperature, be cooled to room temperature again, then take out carbonizing production, using deionized water repeatedly to clean to leacheate is neutrality, dries, finally cross 0.25mm sieve, carry lanthanum charcoal.
2. the preparation method of a kind of year according to claim 1 lanthanum charcoal arsenic-removing adsorption agent, it is characterized in that, in step S2, the amount ratio of maize straw powder, lanthanum chloride solution is 10g:(100-150) mL, wherein in lanthanum chloride solution, the quality of La element and the mass ratio of maize straw powder are 8%-15%; The pH regulating mixed liquor is 10, and mixing time is 60min.
3. the preparation method of a kind of year according to claim 1 lanthanum charcoal arsenic-removing adsorption agent, is characterized in that, in step S2, centrifugal rotational speed is 2000 ~ 5000rpm, and centrifugation time is 2 ~ 10min.
4. the preparation method of a kind of year according to claim 1 lanthanum charcoal arsenic-removing adsorption agent, is characterized in that, in step S2, utilizes the AgNO of 0.1M
3solution detects in leacheate whether there is Cl
-.
5. the preparation method of a kind of year according to claim 1 lanthanum charcoal arsenic-removing adsorption agent, is characterized in that, in step S2, and w (La)/w (stalk)=9.47%; In step S3, design temperature is 300 DEG C, and the retention time is 20min.
6. the lanthanum-carried charcoal obtained by the preparation method of a kind of year lanthanum charcoal arsenic-removing adsorption agent described in any one of claim 1-5.
7. the lanthanum-carried charcoal application in the treatment of waste water obtained by the preparation method of a kind of year lanthanum charcoal arsenic-removing adsorption agent described in any one of claim 1-5, applied environment is acid.
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