CN110449114A - A kind of preparation method and application for mixing aluminium eakleite material - Google Patents
A kind of preparation method and application for mixing aluminium eakleite material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and application for mixing aluminium eakleite material, by by Ca (OH)2Powder is add to deionized water, and is uniformly mixed, secure satisfactory grades scattered suspending liquid A；Then by SiO2Powder is added in KOH, and deionized water is then added, and is uniformly mixed, secure satisfactory grades scattered suspension B；Again under ultrasonic continuous effect, high dispersion suspensioning liquid B is slowly dropped in high dispersion suspensioning liquid A, NaAlO is slow added into2Solution, then foaming agent is added, ultrasonic reaction is aged later, and obtained product is washed, and is dried, and grinding, sieving obtains mixing aluminium eakleite powder.The present invention mixes AlO during preparing eakleite using sonochemical method for the first time2 ‑Substitute the SiO in eakleite3 2‑Aluminium eakleite is mixed in preparation, which can heavy metal lead in efficient absorption waste water.
Description
Technical field
The present invention relates to field of material synthesis technology, more particularly to a kind of preparation for mixing aluminium eakleite material
Method and application.
Background technique
With the propulsion of rapid development of economy and process of industrialization, the demand to non-ferrous metal increases year by year, has caused
Color heavy metal pollution ecological environment has become current important environmental problem, largely encroaches on mankind's healthy living quality,
Various countries are caused to pay high attention to.Lead can be accumulated in liver and kidney, and Hb synthesis obstrurtion is caused anaemia occur, interfere body
Biochemistry and physiological activity, be discharged into natural water since industrial lead waste water is below standard in Hunan China some areas and seriously endanger
And local mankind's healthy living, a lot of blood lead events occur.At present the processing method of lead waste water mainly have chemical precipitation method, from
Sub- exchange process, membrane separation process, bioanalysis, electrocoagulation, absorption method etc..Chemical precipitation method cost is relatively low but easily to environment cause two dirt
Dye；Ion-exchange has multi-selection but operating cost is high；Although membrane separation technique, bioanalysis and electrocoagulation efficiency it is higher but
The deficiencies of complicated for operation and at high cost equal.Absorption method is cheap because its material is easy to get, and removal effect is good, and reproducibility is strong, useless
Water treatment field embodies green idea and receives much attention.
Eakleite [Ca6Si6O17(OH)2] it is that cavernous structure has biggish specific surface area, it is a kind of good thermal insulating material
Material, is widely used in the industries such as mining industry, electric power, building.Eakleite Some Domestic scholar prepares eakleite using hydro-thermal method,
It is obvious that trial is used for processing part heavy metal-containing waste water effect, has higher removal rate, material condition is harsh, produces due to preparing
Rate is low, bad dispersibility and inhibits it in environmental improvement expanded application the factors such as heavy metal ion adsorbed capacity is low.
Therefore, the removal for how improving dispersibility, the internal pore structure of eakleite to effectively improve it to heavy metal
Rate and adsorbance, the technical issues of becoming those skilled in the art's urgent need to resolve.
Summary of the invention
In view of this, the present invention is using sonicating the present invention provides a kind of preparation method for mixing aluminium eakleite material
Method mixes AlO during preparing eakleite for the first time2 -Substitute the SiO in eakleite3 2-Aluminium eakleite is mixed in preparation
(abbreviation Al-CSH), the material can heavy metal leads in efficient absorption waste water.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method for mixing aluminium eakleite material, comprising the following steps:
1) high dispersion suspensioning liquid A is prepared: by Ca (OH)2Powder is add to deionized water, and is uniformly mixed, and securing satisfactory grades, it is outstanding to dissipate
Supernatant liquid A；
2) high dispersion suspensioning liquid B is prepared: by SiO2Powder is added in KOH, and deionized water is then added, and is uniformly mixed,
Secure satisfactory grades scattered suspension B；
3) it mixes the preparation of aluminium eakleite material: under ultrasonic continuous effect, high dispersion suspensioning liquid B being slowly dropped to
In high dispersion suspensioning liquid A, it is slow added into NaAlO2Solution, then foaming agent is added, ultrasonic reaction 30-35min is aged later
24-26h washs obtained product, dries, and grinding, sieving obtains mixing aluminium eakleite powder.
Preferably, in the preparation method according to molar ratio n (Ca)/n (Si+Al)=1.0-2.0, n (Al)/n (Si+Al)=
5% stoichiometry adds Ca (OH)2、SiO2、NaAlO2。
Preferably, in the step 3) in the case where 50~60 DEG C of ultrasonic continuous act on, high dispersion suspensioning liquid B is slowly dripped
It is added in high dispersion suspensioning liquid A.
Preferably, the foaming agent is NH4HCO3Or urea.
Preferably, successively using dilute hydrochloric acid, deionized water and dehydrated alcohol washing in the step 3).
It is another object of the present invention to which the aluminium eakleite material of mixing of above-mentioned preparation is applied to processing waste water, waste water is removed
In lead, cadmium, copper, zinc, chromium, holding pH value be 4.5-5.5.
It can be seen via above technical scheme that compared with prior art, the present invention has the beneficial effect that:
The present invention is based on sonochemical methods, during preparing eakleite, mix AlO for the first time2-It substitutes in eakleite
SiO3 2-Aluminium eakleite (abbreviation Al-CSH) is mixed in preparation, preparation material technology program is simple and yield high (yield is in 88%-
95%) it, and realizes and changes its internal pore structure and increasing specific surface area, while improving the dispersibility of particle and reducing its crystallization
Degree, effectively improves eakleite to the contact surface and adsorption site of heavy metal-containing waste water, effectively promotes it to weight in waste water
The removal rate and adsorption capacity of metal ion.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawing is eakleite (CSH) and mixes the infrared spectrum characterization result of aluminium eakleite (Al-CSH)；
Fig. 2 attached drawing is the scanning electron microscope map of Al-CSH；
Fig. 3 attached drawing is the energy spectrum diagram of Al-CSH；
Fig. 4 attached drawing is the X diffraction pattern of Al-CSH sample；
Fig. 5 attached drawing is the existing forms of Pb ion；
Fig. 6 attached drawing is the influence that pH adsorbs Pb to Al-CSH；
Fig. 7 attached drawing is influence of the Al-CSH dosage to absorption Pb (II)；
Fig. 8 attached drawing is that Pb initial concentration influences adsorption effect under different temperatures；
Fig. 9 attached drawing is action time to adsorb Pb (II) to Al-CSH to influence；
Figure 10 attached drawing is Langmuir isothermal adsorption model of fit；
Figure 11 attached drawing is Freundlich isothermal adsorption model of fit；
Figure 12 attached drawing is D-R isothermal adsorption model of fit；
Figure 13 attached drawing is quasi- First order dynamic model；
Figure 14 attached drawing is quasi- second order dynamic model；
Figure 15 attached drawing is weber-Mrris kinetic model；
Figure 16 attached drawing is 16 Elovich kinetic models；
Figure 17 attached drawing is lnK0With T-1Linear figure；
Figure 18 attached drawing is the reproducibility for adsorbing Pb (II) Al-CSH afterwards.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment (for adsorbing the lead in waste water)
One, aluminium eakleite material is mixed in preparation
According to molar ratio n (Ca)/n (Si+Al)=1.0, n (Al)/n (Si+Al)=5% stoichiometry, 50~60
Under the effect of DEG C ultrasonic continuous, high dispersion suspensioning liquid B (is weighed into 0.095mol SiO21.0g KOH is added in powder, is added
100ml deionized water) it is slowly dropped to high dispersion suspensioning liquid A and (weighs 0.1mol Ca (OH)2100ml deionization is added in powder
Water) in, it is slow added into 50ml 0.1mol/L NaAlO2Solution.8.0gNH is added4HCO3As foaming agent, ultrasonic reaction
30min is aged for 24 hours later.Obtained product is successively washed with dilute hydrochloric acid, deionized water and dehydrated alcohol, is dried, grinding,
Sieving obtains Al-CSH powder (mixing aluminium eakleite powder).
Two, it is tested using new material of a variety of characterization methods to above-mentioned preparation, optimizes the factor of Adsorption Effect, into one
Step explanation mixes aluminium eakleite to the absorption property and absorption mechanism of Pb (II).
1, reagent and instrument
Experiment agents useful for same is that analysis is pure, and 1g/LPb (II) stock solution is by analytically pure Pb (NO3)2Deionized water is added to match
It makes, other Pb (II) concentration are diluted by stock solution and obtained.
Major experimental instrument: Autosorb iQ type specific surface area and pore structure tester (Kang Ta instrument company, the U.S.),
EVO10 scanning electron microscope band power spectrum (Zeiss, Germany company), (Japanese Rigaku is public for 600 type X diffractometer of Rigaku MiniFlex
Department), PH330i type precision acidity meter (German WTW company), (the general analysis in Beijing is general for TAS-990AFG atomic absorption spectrophotometer
Instrument Co., Ltd), AD-6 autoelectrinic balance (PE company, the U.S.).
2, the characterization of aluminium eakleite sample is mixed
The BET specific surface area and pore-size distribution of sample pass through N on adsorption instrument2Determining adsorption, specific surface area use the side BET
Journey is by N2Adsorption isotherm acquires.The material phase analysis of sample measures on X-ray diffractometer, the condition of test are as follows: Cu target activation
Ka radiation is radiographic source, and scanning range is 10~80 ° (2 θ), and scanning speed is 4 °/min.With the table of scanning electron microscopic observation sample
Face form.
3, experimental method
It pipettes in 100mL 200mg/L Pb (II) simulated wastewater merging 250mL conical flask, adjusts soda acid with HCl and NaOH
Property, be added 0.06gAl-CSH, be placed on oscillator and vibrate, constant temperature 313K, oscillation rate 150r/min, react 60min after from
Heart separation, takes supernatant to measure remnants Pb (II) content.Removal rate ρ (%) and adsorption capacity Q is calculated separately as the following formulae(mg/
G):
ρ=(C0-Ce)/C0× 100% (1)
Qe=(C0-Ce)V/m (2)
In formula, C0For Pb (II) initial concentration (mg/L), CeFor Pb (II) equilibrium concentration (mg/L) after absorption, V is solution body
Product (L), m are Al-CSH dosage (g).
Three, results and discussion
1, material characterization
It to pure eakleite (CSH) and mixes the specific surface area of aluminium eakleite (Al-CSH) and porosity characterizes, surveys
It obtains its specific surface area, average pore size and average Kong Rong and is shown in Table 1.Referring to the classification of porous mass material, aperture is in 2~20nm
Mesoporous (i.e. mesoporous) illustrates that eakleite is mesoporous material, there is large specific surface area, aperture and Kong Rong, is a kind of good
Adsorption functional material.Table 1 is as can be seen that modified Al-CSH specific surface area, the summary of Kong Rong and aperture than unmodified CSH
Greatly, illustrate that eakleite can create more preferable absorption environment by modified, advantage is had more to absorption heavy metal, therefore, this research will
Modified Al-CSH is selected to carry out adsorption experiment to lead ion.
Specific surface area, aperture and the hole of 1 CSH and Al-CSH sample of table hold detection data
Eakleite (CSH) and the infrared spectrum characterization result of aluminium eakleite (Al-CSH) is mixed as shown in Figure 1, infrared light
Spectrogram shows that the structure of modified material is not destroyed, and basic framework still saves.3300-3700cm-1Bands of a spectrum are stretching for-OH
Contracting vibration absorption peak, 714.4cm-1And 1081.7cm-1Bands of a spectrum be respectively present Si-O-Si key symmetrical stretching vibration absorption peak and
Different degrees of offset occurs for asymmetric stretching vibration absorption peak, two peaks of Si-O-Si key, there is to a certain degree peak intensity at two
Weaken, the reason is that due to AlO2 -Instead of the part SiO in eakleite3 2-It causes.
As shown in the scanning electron microscope map of Fig. 2A l-CSH, sample shape leads to table similar to needle wadding fiber, the needle-shaped development in surface
Face is extremely coarse, is conducive to adsorbate in solution and quickly contacts and be adsorbed with the active site on the surface Al-CSH, illustrates the material
Material is a kind of good adsorbent material.
As can be seen that synthesis eakleite specimen material main component is Ca, Si, O from Fig. 3 energy spectrum diagram (EDX), aluminium is mixed
Eakleite energy spectrum diagram significantly increases Al element peak, and Si element peak slightly weakens, and illustrates AlO2 -Successfully it is doped in CSH lattice
In, it is substitution part SiO3 2-Form new eakleite derivative.
Further, it is analyzed using crystal structure of the X diffraction to Al-CSH, as a result as shown in Figure 4.Al-CSH particle
XRD spectrum 2θ=20.8 °, 26.7 °, 29.4 ° nearby show diffraction maximum, kiss substantially with the standard diffraction figure of eakleite
It closes.Simultaneously 2 in figureθThere is AlO at=23.0 °, 36.0 °, 36.5 °2 -Characteristic absorption peak, declaratives AlO2 -Into hard silicon
The lattice of calcium stone is instead of SiO3 2-, so that the crystallinity of particle declines, agglomeration weakens.
2, influence of the pH value to adsorption effect
From figs. 5 and 6, it can be seen that, as pH increases, Al-CSH is to Pb removal rate and suction in the range of pH=1.5~5.5
Attached capacity constantly rises, and main cause is that there are a large amount of H during solution acidic is strong+With Pb2+Competitive Adsorption is formed, because of H+Very
It is easy to be adsorbed and quickly capture Al-CSH adsorbent surface adsorption site, so that adsorbent surface positive charge increases, with the same sex
Pb2+Generate repulsion, it is suppressed that Pb2+By exchange and surface complexing, so as to cause Al-CSH to Pb2+Adsorption efficiency with pH value
It reduces and is remarkably decreased.As pH=5.5, removal rate reaches up to 95.58%.Continue increase solution ph, removal rate and
Adsorption capacity is then gradually reduced, the reason is that as pH > 5.5, OH in solution-Increase, is easy to make Pb (II)+Hydrolysis become strong, cause
Pb2+Quickly to Pb (OH)3+、Pb(OH)+、Pb4(OH)4 4+Deng transformation, these positively charged ionic state lead hydroxide compounds with
Pb2+The identical generation of charge is repelled, and Pb is inhibited2+It reaches the surface Al-CSH and is adsorbed, to reduce suction of the Al-CSH to Pb (II)
Attached ability.PH is further increased, Pb (OH) then occurs in solution2Precipitating, is less useful for Pb (II) and is adsorbed.Therefore, the present invention couple
Controlling in pH value is 4.5-5.5, and optimal is 5.5.
3, Al-CSH dosage influences Pb adsorption effect
According to experimental method, adjusts adsorbent amount and compare experiment, Pb (II) removal efficiency is with absorption in solution
The variation of agent Al-CSH dosage is seen from Fig. 7 such as Fig. 7, as Al-CSH dosage increases, to the removal rate of Pb (II) by increasing rapidly
To being slowly increased, and adsorption capacity variation tendency is to be dropped rapidly to slow reduction on the contrary, with similar adsorbent material Adsorption law
It is almost the same.Al-CSH additive amount increases to 0.06g from 0.02g, and removal rate is increased to 95.58% from 83.77%, adsorption capacity
318.48mg/g then is dropped to from 837.7mg/g, is reduced fairly obvious.Al-CSH dosage continues to increase to 0.12g, removal rate and absorption
Capacity is respectively 98.07% and 163.44mg/g, only increases by 2.52% with dosage for the removal rate of 0.06g adsorbent, absorption is held
Amount then reduces 155.04mg/g.It is comprehensively compared, under the premise of ensuring higher removal rate and relatively large adsorption capacity, present invention absorption
Agent dosage is advisable using 0.06g.
4, Pb initial concentration influences adsorption effect
According to experimental method, the control of adsorption experiment temperature in 293,303 and 313K, change Pb (II) initial concentration (60~
Adsorption experiment 300mg/L) is carried out, Al-CSH is carried out and Fig. 8 is shown in Pb (II) absorption result.As seen from Figure 8, as Pb (II) is initial
Concentration constantly increases, and Al-CSH embodies continuous reduction to Pb (II) removal rate at three temperature, and the high ratio temperature of temperature is low
Removal rate is high, illustrates in certain temperature range, increases temperature and is conducive to Al-CSH to Pb (II) removal.In addition also illustrate the absorption
Chemisorption should also occur other than physical absorption for mechanism, promote Al-CSH and Pb (II) to combine by external energy, thus
Pb (II) is promoted to be efficiently removed.
5, action time influences Pb (II) adsorption effect
According to experimental method, Al-CSH is carried out at 293,303 and 313k respectively, adsorption experiment is compared to Pb (II), gone
Except rate is with action time variation tendency such as Fig. 9.It can be seen in fig. 9 that adsorbing preliminary stage in 5~60min, Al-CSH is to Pb (II)
Removal rate rises quickly, and removal rate is increased to 90% or more from 70%, illustrates that the rate of adsorption is quite fast；When continuing to extend absorption
Between, the later stage from 60min to 300min, Al-CSH gently rises Pb (II) removal rate and adsorption capacity, at three temperature
Removal rate increase separately only 1.5%, 1.67% and 2.28%, increase unobvious, illustrate that Al-CSH makees Pb (II)
With 60min just close to adsorption equilibrium, extends adsorption time and have little significance to adsorption effect is improved.Reason adsorbs preliminary stage, greatly
Since electrostatic interaction is attracted to the surface Al-CSH, ion exchange and surface occur part Pb (II) for part lead ion and calcium ion
Complexing；The later period is adsorbed, causes adsorption capacity to weaken since adsorbent surface adsorption site is largely occupied by Pb (II), so that absorption
Rate slows down.Therefore, the suction-operated time control 60min of this research is preferred.
In addition it should be pointed out that the research of Al-CSH dosage, action time and Pb initial concentration is only further described
The adsorption effect of Al-CSH material, and in practical applications, it is also necessary to appropriate adjustment is carried out according to the concentration of heavy metal in waste water.
6, adsorption mechanism research
6.1 adsorption isotherm
Equilibrium adsorption thermoisopleth is to reflect that adsorbent to the important method of adsorbate characterization of adsorption, can be used for describing different flat
Adsorption capacity under the concentration that weighs, and pass through the saturated adsorption capacity of the available adsorbent of fitting to adsorption process.It is common etc.
Warm equation has Langmuir isotherm formula (3), Freundlich isotherm formula (4) and Dubinin-Radushkevich (D-R) isothermal
Formula (5).
Qe=QmKLCe/(1+KLCe) (3)
Qe=KFCe 1/n (4)
In formula, CeIt is the concentration (mg/L) of Pb (II) in the solution adsorbed when reaching balance, QeWhen being that absorption reaches balance
Adsorption capacity (mg/g), QmIt is maximal absorptive capacity (mg/g), KLIt is absorption constant (L/mg) relevant to adsorption energy, KFIt is with 1/n
Freundlich constant.
lnQe=lnXm- k ε2 (5)
ε=RTln (1+Ce -1) (6)
E=(2k)-1 (7)
In formula, CePb (II) concentration (mol/L) in solution when for adsorption equilibrium, k is model constants relevant to free energy,
XmFor the monolayer adsorption amount (mol/g) of adsorbent, ε is Polanyi energy (kJ/mol), and R is the normal kJ/ (mol of Pu Shi gas
K), T is temperature (K), and E is that absorption average free energy changes (KJ/mol).
According to adsorption isotherm experiment data, Al-CSH is adsorbed using Langmuir, Freundlich, D-R Isothermal Model
The process of Pb is fitted, and as shown in figs. 10-12, fitting parameter the results are shown in Table 2 to fitting result schematic diagram.Compare three isothermal moulds
Type fitting result, in scope of experiment, the fitting correlation coefficient of each Isothermal Model can be higher than 0.9, illustrate these three isothermal moulds
Type can reflect the absorption behavior, and wherein Langmuir Isothermal Model related coefficient highest, is above 0.98, show Langmuir etc.
Temperature model is most suitable for describing the adsorption process, discloses this and is adsorbed as mono layer adsorption.Freundlich isotherm formula constant KFValue
Larger and 1/n value illustrates that Al-CSH is adsorbed as preferential absorption to Pb less than 1.The absorption average free energy that D-R Isothermal Model calculates
Changing E value is respectively 128.21,147.06,166.67kJ/mol, illustrates that there are ions for suction-operated of the Al-CSH to Pb (II)
The adsorpting characteristics such as exchange and surface complexing.
Al-CSH is to Pb (II) isothermal adsorption parameter list under 2 different temperatures of table
Saturated adsorption capacity Q of the Al-CSH to Pb (II) absorption Langmiur model under different temperaturesmIt can be seen that temperature
High corresponding QmGreatly, illustrate that temperature raising is conducive to adsorption reaction progress.Al-CSH adsorbs the saturation of Pb (II) and holds when 313K
Amount is up to 497.99mg/g, is saturated heat-sinking capacity comparing result such as table 3, this research with recent document report absorption Pb (II) material
Al-CSH adsorbent material has a clear superiority.
3 Al-CSH of table is with other adsorbents to the contrast table of Pb (II) adsorption capacity
6.2 adsorption dynamics adsorption kinetics
Further to investigate Al-CSH to the absorption mechanism of the Pb (II) in solution, it is utilized respectively Lagergren pseudo-first-order
The power such as (formula 8), the quasi- second level of Lagergren (formula 9), Weber-Morris diffusion (formula 10) and Elovich (formula 11)
Learn model.
Qt=Qe(1-e-K1t) (8)
Qt=Qe 2K2t/(1+QeK2t) (9)
Qt=Kit1/2+C (10)
Qt=1/ βeln(αeβe)+1/βelnt (11)
In formula, QtIt is the adsorbance (mg/g) of t moment, K1It is pseudo-first-order adsorbing filament technique (min-1), K2It is that quasi- second level is inhaled
Attached rate constant [mg/ (gmin)]；KiFor interior diffusion adsorbing filament technique (mg/gmin1/2), C is constant；αe[mg/(g·
It min)] is initial absorbing rate constant, βeIt (g/mg) is desorption rate constant.
The experimental data for adsorbing Pb (II) at 293,303 and 313K to Al-CSH respectively, which is fitted, sees Figure 13-16 institute
Show, fitting result such as table 4.
Table 4 is fitted kinetic parameters
Adsorption experiment data are fitted, the results are shown in Table 4.Compare four kinds of dynamics fitting parameters the results show that
Wherein pseudo-second order kinetic models fitting effect is best, coefficient R2Reach 0.99 or more, and pseudo-second order kinetic equation meter
Obtained theoretical adsorption capacity Qe,calWith the obtained end value Q of experimente,expIt is very identical, it is good at describing Al-CSH to Pb
(II) absorption, while this absorption is also embodied with chemisorption behavior.Weber-Morris diffusion (inside diffusion)
Parameter intercept is not equal to zero in model of fit, and straight line does not pass through origin, and illustrating internal diffusion process not is the single control of the rate of adsorption
Step processed may infer that the absorption should be comprising multiple effects as spread inside external Liquid film diffusion, adsorption and particle
Comprehensively control process；In addition, the K of internal diffusion equationiIt is reduced as temperature increases, to the equilibrium adsorption capacities of Pb (II)
It increases accordingly, illustrates that the adsorption process increases temperature and is conducive to adsorption reaction progress, the removal to Pb (II) can be effectively improved.
Elovich is fitted to obtain model slope and intercept is relatively large, shows that Al-CSH is very fast to the adsorption rate of Pb (II) and adsorbs
Ability is strong.
6.3 Adsorption thermodynamics researchs
Adsorption thermodynamics reflect the fuel factor of the adsorption process under isothermal and isobaric, embody neither endothermic nor exothermic feature, indirectly
Ground reflects that it could spontaneous carry out state.Adsorption thermodynamics major parameter Gibbs free energy (Δ G), enthalpy change (Δ H) and Entropy Changes
(Δ S), the positive or negative value of Δ G can be determined that whether reaction spontaneous can carry out, and the positive or negative value judgement reaction of Δ H belongs to heat absorption
Or exothermic process.Thermodynamic parameter value is calculated by formula 12~15 and is obtained:
Δ G=Δ H-T Δ S (12)
Δ G=-RTlnK0 (13)
lnK0=1000*C0*lnKL (14)
lnK0=-Δ H/ (RT)+Δ S/R (15)
In formula, R is gas constant [J/ (molK)], and T is absolute temperature (K), K0It is being adsorbed for characterization Pb (II) distribution
The equilibrium constant (the where K of agent and solution0is the equilibrium constant characterizing the
distribution of lead ions between the solution phase and the phase of the
Adsorbent material), KLFor Langmiur constant.
Make lnK0With 1/T linear regression, as shown in figure 17, linear fit equation is y=Y=-5212X+27.33, related
Coefficients R2=0.9890, Gibbs free energy (Δ G), enthalpy change (Δ H) and the entropy of virtual condition are calculated further according to formula (16), (17)
Become (Δ S), is shown in Table 5.As can be seen from Table 5, Δ G is negative value in thermodynamic parameter, illustrates Al-CSH to the Pb in solution
(II) it is adsorbed as spontaneous progress；Enthalpy change numerical value can be used to judge the type of absorption, and chemisorption process enthalpy change is typically larger than
60KJ/mol, the enthalpy change of physical absorption are generally then less than 40KJ/mol.Al-CSH adsorbs Δ H to Pb (II) and is greater than 40KJ/mol,
The absorption is an endothermic reaction process, illustrates that increasing temperature is conducive to adsorption reaction progress, Al-CSH is to Pb (II) adsorption machine
Reason is the synthesis absorption behavior of ion exchange, surface complexing and physical absorption, basic with front isotherm adsorption model estimation result
Unanimously.Entropy Changes is that positive value indicates that the adsorption process scrambling increases.
Thermodynamic parameter under 5 different temperatures of table
7, reproducibility
Desorption processing is carried out to the Al-CSH sample after absorption Pb (II) using 50ml 0.1mol/L hydrochloric acid, after desorption
For sample through deionized water washing and filtering 4 times, 70 DEG C of drying continue Pb (II) adsorption experiment further in accordance with experimental method, successively
Step is repeated 5 times, and experimental result is as shown in figure 18.From desorption-sorption cycle experiment as can be seen that after regeneration 5 times, Al-CSH
Still keeping higher removal rate to the absorption of Pb (II) is 88.67%, only has dropped 6.88%, absolutely proves the material regeneration energy
Power and strong shock resistance are a kind of materials of good adsorption properties.
To sum up, the present invention combine ultrasound and doping techniques synthesize for the first time mix aluminium eakleite be applied to simulate lead waste water at
Reason, experiments have shown that removal effect is obvious, it is obviously more superior than recent report same type of material adsorption effect, it is worth promoting very much and answers
With.
Further, in the case where pH 5.5, temperature 313K, action time 60min etc. optimize experiment condition, dosage 0.06gAl-
For CSH to the removal rate of 100mL 200mg/LPb (II) up to 95.55%, equilibrium adsorption capacities are up to 318.48mg/g.
Adsorption isotherm model shows that Langmuir models fitting related coefficient is up to 0.99, is most suitable for Al-CSH pairs of description
The adsorpting characteristic of Pb (II), the maximum adsorption capacity under 313K is respectively 497.99mg/g, has fully demonstrated stronger adsorption energy
Power.For D-R Isothermal Model to 293,303 and 313K fitting experimental data, corresponding activation energy value is larger, reflects Al-CSH
To the suction-operated of Pb (II), there are the absorption behaviors that ion exchange and surface are complexed.
For pseudo-second order kinetic models fitting Al-CSH to the adsorption process of Pb (II), related coefficient, most can energy higher than 0.99
Al-CSH is embodied to the absorption behavior of Pb (II).Thermodynamic parameter shows that this is adsorbed as the spontaneous endothermic reaction, and temperature increases advantageous
In removal of the Al-CSH to Pb (II).
It is fitted the result of isotherm adsorption model, kinetic model and thermodynamic parameter, it was demonstrated that Al-CSH adsorbs Pb (II)
The synthesis absorption behavior that mechanism is mainly combined with ion exchange, surface complexing and physics.
In addition, other heavy metals have also been made in the present invention, (adsorbent amount 0.06g, heavy metal are initially dense under similarity condition
Spend 200mg/L, volume 100ml, reaction time 60min, temperature 313K, pH5.5) absorption comparison, as cadmium (removal rate 88.54%,
Adsorption capacity 135.9mg/g), copper (removal rate 89.63%, adsorption capacity 149.38mg/g), zinc (removal rate 89.35%, absorption
Capacity 138.92mg/g), the waste water such as chromium (removal rate 85.47%, adsorption capacity 127.45mg/g), wherein to lead under similarity condition
Waste water removal rate and adsorption capacity are maximum
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (7)
1. a kind of preparation method for mixing aluminium eakleite material, which comprises the following steps:
1) high dispersion suspensioning liquid A is prepared: by Ca (OH)2Powder is add to deionized water, and is uniformly mixed, secure satisfactory grades scattered suspension
A；
2) high dispersion suspensioning liquid B is prepared: by SiO2Powder is added in KOH, and deionized water is then added, and is uniformly mixed, is secured satisfactory grades
Dissipate suspension B；
3) it mixes the preparation of aluminium eakleite material: under ultrasonic continuous effect, high dispersion suspensioning liquid B being slowly dropped to high score
It dissipates in suspending liquid A, is slow added into NaAlO2Solution, then foaming agent is added, ultrasonic reaction 30-35min is aged 24- later
26h washs obtained product, dries, and grinding, sieving obtains mixing aluminium eakleite powder.
2. a kind of preparation method for mixing aluminium eakleite material according to claim 1, which is characterized in that the preparation method
According to molar ratio n (Ca)/n (Si+Al)=1.0-2.0, n (Al)/n (Si+Al)=5% stoichiometry adds Ca
(OH)2、SiO2、NaAlO2。
3. a kind of preparation method for mixing aluminium eakleite material according to claim 1, which is characterized in that the step 3)
In in the case where 50~60 DEG C of ultrasonic continuous act on, high dispersion suspensioning liquid B is slowly dropped in high dispersion suspensioning liquid A.
4. a kind of preparation method for mixing aluminium eakleite material according to claim 1-3, which is characterized in that institute
Stating foaming agent is NH4HCO3Or urea.
5. a kind of preparation method for mixing aluminium eakleite material according to claim 4, which is characterized in that the step 3)
In successively using dilute hydrochloric acid, deionized water and dehydrated alcohol washing.
6. it is a kind of by a kind of described in any item preparation method preparations for mixing aluminium eakleite material of claim 1-5 to mix aluminium hard
Application of the silico-calcium stone material in processing lead waste water.
7. a kind of processing method of lead waste water, which is characterized in that the described in any item one kind of claim 1-5 are mixed the hard silico-calcium of aluminium
Stone material preparation method preparation aluminium eakleite material of mixing be added in waste water to be processed, remove waste water in lead, cadmium,
Copper, zinc, chromium, holding pH value are 4.5-5.5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106052A (en) * | 2022-07-19 | 2022-09-27 | 上海应用技术大学 | Sepiolite/montmorillonite composite material and preparation method and application thereof |
| CN116173931A (en) * | 2023-02-01 | 2023-05-30 | 衡阳师范学院 | Polypyrrole-polyaniline modified xonotlite as well as preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987006924A1 (en) * | 1986-05-07 | 1987-11-19 | Japan As Represented By President Of Tohoku Univer | Process for producing xonotlite fibers |
| JPH07247111A (en) * | 1994-03-14 | 1995-09-26 | Rengo Co Ltd | Silver-containing xonotlite |
| CN103693758A (en) * | 2013-12-26 | 2014-04-02 | 同济大学 | Method for treating methylene blue dye wastewater |
| CN109485055A (en) * | 2018-07-18 | 2019-03-19 | 衡阳师范学院 | A kind of eakleite and the preparation method and application and its regeneration for mixing miserite |
| CN109926024A (en) * | 2019-03-27 | 2019-06-25 | 湖南工学院 | A kind of preparation method and applications of magnetism organic modified nano adsorbent material |
| US20190193066A1 (en) * | 2017-12-22 | 2019-06-27 | Mohsen Padervand | Reusable porous Na(Si2Al)O6.xH2O/NiFe2O4 structure for selective removal of heavy metals from waste waters |
-
2019
- 2019-07-23 CN CN201910667257.5A patent/CN110449114B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987006924A1 (en) * | 1986-05-07 | 1987-11-19 | Japan As Represented By President Of Tohoku Univer | Process for producing xonotlite fibers |
| JPH07247111A (en) * | 1994-03-14 | 1995-09-26 | Rengo Co Ltd | Silver-containing xonotlite |
| CN103693758A (en) * | 2013-12-26 | 2014-04-02 | 同济大学 | Method for treating methylene blue dye wastewater |
| US20190193066A1 (en) * | 2017-12-22 | 2019-06-27 | Mohsen Padervand | Reusable porous Na(Si2Al)O6.xH2O/NiFe2O4 structure for selective removal of heavy metals from waste waters |
| CN109485055A (en) * | 2018-07-18 | 2019-03-19 | 衡阳师范学院 | A kind of eakleite and the preparation method and application and its regeneration for mixing miserite |
| CN109926024A (en) * | 2019-03-27 | 2019-06-25 | 湖南工学院 | A kind of preparation method and applications of magnetism organic modified nano adsorbent material |
Non-Patent Citations (2)
| Title |
|---|
| 张建明: "铝掺杂的水化硅酸钙结构及微观形貌研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
| 张建明: "铝掺杂的水化硅酸钙结构及微观形貌研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》, no. 8, 15 August 2011 (2011-08-15), pages 038 - 222 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106052A (en) * | 2022-07-19 | 2022-09-27 | 上海应用技术大学 | Sepiolite/montmorillonite composite material and preparation method and application thereof |
| CN116173931A (en) * | 2023-02-01 | 2023-05-30 | 衡阳师范学院 | Polypyrrole-polyaniline modified xonotlite as well as preparation method and application thereof |
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