CN105107471A - Sulphydryl lignocellulose/montmorillonite composite heavy metal ion adsorbent and preparation and application thereof - Google Patents
Sulphydryl lignocellulose/montmorillonite composite heavy metal ion adsorbent and preparation and application thereof Download PDFInfo
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- CN105107471A CN105107471A CN201510583535.0A CN201510583535A CN105107471A CN 105107471 A CN105107471 A CN 105107471A CN 201510583535 A CN201510583535 A CN 201510583535A CN 105107471 A CN105107471 A CN 105107471A
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Abstract
The invention provides sulphydryl lignocellulose/montmorillonite composite heavy metal ion adsorbent and preparation and application thereof. The adsorbent is formed by sulphydryl lignocellulose and montmorillonite in a composite mode, wherein the mass ratio of sulphydryl lignocellulose to montmorillonite is 1:1-1.5:1, and insertion layers of sulphydryl lignocellulose enter between lamination layers of montomorillonite. The sulphydryl lignocellulose/montmorillonite composite heavy metal ion adsorbent is applied to removing heavy metal in waste water. The preparation method of the sulphydryl lignocellulose/montmorillonite composite heavy metal ion adsorbent has the advantages that preparation is easy, raw materials are easy to obtain, environmental friendliness is achieved, and no secondary pollution occurs; the obtained sulphydryl lignocellulose/montmorillonite composite heavy metal ion adsorbent is free of toxin, capable of being biologically degraded and low in cost and achieves simple and convenient adsorbing operation and a high adsorbing quantity when applied to removing heavy metal ions in waste water.
Description
Technical field
The present invention relates to a kind of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent and preparation and application, belong to technical field of composite materials.
Background technology
The water resources shortage of China, water resource quality also constantly declines.Due to a large amount of discharges of all types of industries waste water from industries such as ore processing, process hides, plating and pigment, wherein a lot of heavy metal ion enters in water, air and soil, and retain with various chemical form, Cumulate Sum migration, this causes huge harm to human environment, and the ecological disruption caused thus and economic loss are also immeasurable.So the improvement of industrial wastewater has caused the concern of whole world various countries.
In recent years, Inner Mongolia, the industry such as mining, plating, metallurgy, pharmacy as Chifeng City, Ordos City, packet header and holder county and other places entered the period increased fast.In people's living environment; a large amount of industrial pollutants such as washes, electroplating wastewater etc. containing various heavy metal ion increase gradually; the economic worth of these industrial wastewaters is higher; but health and the living environment of the Ye Duiwo district people create serious harm; my district government also implements corresponding policies and regulations in order to protect water source, prevention of water body pollution.Nowadays, people have higher requirement to health, environmental protection, sustainable development etc., driven environmental protection thus, the Industrial Wastewater Treatment new material new technological industry that can reuse increases fast.
Traditional heavy metal industrial effluent processing method mainly contains chemical precipitation method, ion-exchange, electrochemical treatment, membrane technology etc., these processing methods achieve good effect to a certain extent, but ubiquity is expensive, settling property is poor, seriously polluted, service life is short, the not easily shortcoming such as regeneration, and these shortcomings make its practical application be very restricted.And absorption method is as a kind of novel heavy metals removal, recovery technology, more and more receive the concern of people.Absorption method mainly utilizes cheap biomaterial heavy metal to adsorb, be particularly useful for the process of low-concentration heavy metal industrial wastewater (<100mg/L), the Novel waste water absorbent of the living beings degradation material comprehensive utilization of this kind of low cost, efficient, nontoxic, reusable edible has the advantages such as the high and adsorption rate of adsorption efficiency is fast, is now extensively paid attention to.
Up to now, structure and material character is mainly laid particular emphasis on to biodegradable polymer (as: starch, pine nut powder, cellulose, glycan, shitosan, cellulose and lignin) and the research of derivative and inorganic clay nano-complex thereof both at home and abroad, research great majority about degradable natural high molecular polymer/inorganic clay nanocomposites lay particular emphasis on the aspect of performances such as mechanics, thermodynamics and gas barrier, less to the report of heavy metals in industrial wastewater ionic adsorption and desorption performance, and the theory not forming system carrys out Instructing manufacture practice.Prior art for lignocellulosic and imvite (LNC/MMT) and with the preparation of calcium-base montmorillonite nano composite material and done a large amount of research work to the adsorption-desorption of heavy metal ions in wastewater and dyestuff, but have not been reported containing the heavy metal ion in the preparation of the lignocellulosic/Nano composite material of montmorillonite adsorbent of activity functional groups modification and sorption and desorption industrial wastewater thereof about research.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent.
The present invention also aims to the preparation method that a kind of above-mentioned sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent is provided.
The present invention also aims to provide a kind of above-mentioned sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent removing the application in heavy metal contained by waste water.
For reaching above-mentioned purpose, the invention provides a kind of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent, this adsorbent is formed by sulfydryl lignocellulosic and montmorillonite Composite;
The mass ratio of described sulfydryl lignocellulosic and imvite is 1:1-1.5:1; The mass ratio of preferred sulfydryl lignocellulosic and imvite is 1:1;
Described sulfydryl lignocellulosic intercalation enters between the lamella of described imvite.
According to the preferred embodiment of the present invention, the granularity of described sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent is 150-200 order.
Present invention also offers the preparation method of above-mentioned sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent, this sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent is prepared by solution in-situ intercalated polymerization, and the method comprises the following steps:
A, sulfydryl lignocellulosic is added in sodium hydrate aqueous solution, obtain the suspension of sulfydryl lignocellulosic;
B, imvite to be added to the water, to obtain the suspension of imvite;
C, joined by the suspension of described imvite in the suspension of sulfydryl lignocellulosic, heating makes it react, and by product washing to neutral, after drying, obtains described sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent.
According to the preferred embodiment of the present invention, the mode of " in batches adding " is adopted to join in sodium hydrate aqueous solution by sulfydryl lignocellulosic in step a, the object herein " in batches added " is to make sulfydryl lignocellulosic be dissolved in alkali lye better, disposablely to add, need to stir for a long time, experimental implementation can waste time and energy, so add the carrying out operating and be more convenient for testing in batches.The present invention does not have specific requirement to the charging times of " adding " and each feeding quantity in batches, and those skilled in the art can need to select suitable charging times and each addition to feed in raw material according to field operation.
According to the preferred embodiment of the present invention, the concentration of sodium hydrate aqueous solution described in step a is 0.1-0.2mol/L.
According to the preferred embodiment of the present invention, the ratio of the quality of the lignocellulosic of sulfydryl described in step a and the volume of sodium hydrate aqueous solution is 1:30-1:35, and unit is respectively g and mL; The ratio of the preferred described quality of sulfydryl lignocellulosic and the volume of sodium hydrate aqueous solution is 1:30, and unit is respectively g and mL.
According to the preferred embodiment of the present invention, the mass ratio of the lignocellulosic of sulfydryl described in step b and imvite is 1:1-1.5:1, is preferably 1:1; The ratio of the quality of imvite described in step b and the volume of water is 1:30-1:40, and be preferably 1:30, unit is respectively g and mL.
According to the preferred embodiment of the present invention, the temperature adding thermal response described in step c is 60-65 DEG C, and the reaction time is 6-8h; The temperature adding thermal response is preferably 60 DEG C, and the reaction time is 8h.
According to the preferred embodiment of the present invention, drying described in step c is 100-110 DEG C of dry 8-10h; Preferred described drying is 105 DEG C of dry 8h.
According to the preferred embodiment of the present invention, described sulfydryl lignocellulosic is obtained by the alcoholic extract hydroxyl group generating portion esterification of TGA and lignocellulosic, and its concrete preparation method is as follows:
TGA and acetic anhydride are mixed, after cooling, adds lignocellulosic, react under water-bath, then by product washing to neutral post-drying, obtain described sulfydryl lignocellulosic.
According to the preferred embodiment of the present invention, in the preparation process of sulfydryl lignocellulosic, described in be cooled to and be cooled to room temperature.
According to the preferred embodiment of the present invention, in the preparation process of sulfydryl lignocellulosic, the temperature of described water-bath is 40-45 DEG C, and the reaction time is 45-48h;
The temperature of preferred described water-bath is 40 DEG C, and the reaction time is 45h.
According to the preferred embodiment of the present invention, in the preparation process of sulfydryl lignocellulosic, the temperature of described oven dry is 40-50 DEG C, and the temperature of preferred described oven dry is 40 DEG C.
Present invention also offers above-mentioned sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent and remove the application in heavy metal contained by waste water.
The preparation method of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent of the present invention with the abundant lignocellulosic (LNC) in Inner Mongolia Autonomous Region and imvite (MMT) for raw material, sulfydryl lignocellulosic (SH-LNC) is obtained by carrying out thiol chemistry modification to lignocellulosic, again SH-LNC and MMT (it has nanoscale lamellar structure) is carried out in-situ intercalated polymerization, sulfydryl lignocellulosic intercalation enters in the nanoscale lamellar structure of imvite, prepare sulfydryl lignocellulosic/imvite (SH-LNC/MMT) nano composite material first, i.e. sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent.Preparation method of the present invention achieves sulfydryl lignocellulosic and the combination of imvite on nanoscale, make hydrophilic clay mineral surface-hydrophobicized, also reduce the surface energy of clay mineral through organic-treating simultaneously, enhance the compatibility between lamella and polymer molecular chain, improve the boundary moisture effect between mineral and polymer, further increase the interface affinity between inorganic phase and organic phase; In addition, existence the be combineding with each other advantageously between lignocellulosic and imvite of sulfydryl, it exists and also can promote the solubility of imvite to weaken imvite suspending power in the solution, makes it can be dissolved in better in solution and can Adsorption of Heavy Metal Ions better.
The preparation method of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent of the present invention with the abundant lignocellulosic (LNC) in Inner Mongolia Autonomous Region and imvite (MMT) for raw material, wherein, LNC extensively exists at nature, and have biodegradability, and MMT is at Inner Mongolia Autonomous Region rich reserves, A wide selection of colours and designs and cheap.
In addition, preparation method of the present invention has that preparation is simple, raw material is easy to get, and environmentally friendly, does not cause the features such as secondary pollution, has huge economic and social benefit.
Sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent of the present invention is nontoxic, biodegradable and with low cost, this adsorbent has isomorphous substitution phenomenon between activity functional groups on chelation group (-SH), LNC molecular skeleton and montmorillonite layer simultaneously, something which increases the adsorption effect of heavy metal ion in this Adsorbent For Removal of Heavy.
Be used for removing the heavy metal ion contained in waste water by sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent of the present invention, the adsorption operations of this adsorbent is easy, and adsorbance is high.
Accompanying drawing explanation
Fig. 1 is the standard working curve figure in application examples 1;
Fig. 2 is the curve map between the initial concentration of Fe (III) in application examples 1 and SH-LNC/MMT adsorbent Fe (III) adsorbance;
Fig. 3 is the curve map in application examples 1 between solution ph and SH-LNC/MMT adsorbent Fe (III) adsorbance;
Fig. 4 is the curve map in application examples 1 between adsorption temp and SH-LNC/MMT adsorbent Fe (III) adsorbance;
Fig. 5 is the curve map in application examples 1 between adsorption time and SH-LNC/MMT adsorbent Fe (III) adsorbance;
Fig. 6 is in application examples 1 under different Fe (III) initial concentration, the curve map between adsorption time and SH-LNC/MMT adsorbent Fe (III) adsorbance;
Fig. 7 is 640mg/L in solution concentration in application examples 1, when adsorption temp is 40 DEG C, and the pseudo-first-order kinetic model figure of SH-LNC/MMT adsorbent Fe (III);
Fig. 8 is 640mg/L in solution concentration in application examples 1, when adsorption temp is 40 DEG C, and the pseudo-second order kinetic illustraton of model of SH-LNC/MMT adsorbent Fe (III);
Fig. 9 is in application examples 1 under different adsorption temp (35 DEG C, 40 DEG C, 45 DEG C), the curve map between Fe (III) initial concentration and SH-LNC/MMT adsorbent Fe (III) adsorbance;
Figure 10 is in application examples 1 be 520mg/L, 560mg/L, 600mg/L, 640mg/L, 680mg/L in solution concentration, adsorption time is 40min, adsorption temp is under the condition of 40 DEG C, the Langmuir isotherm adsorption model figure of SH-LNC/MMT adsorbent Fe (III);
Figure 11 is in application examples 1 be 520mg/L, 560mg/L, 600mg/L, 640mg/L, 680mg/L in solution concentration, adsorption time is 40min, adsorption temp is under the condition of 40 DEG C, the Freundlich isotherm adsorption model figure of SH-LNC/MMT adsorbent Fe (III);
Figure 12 is the standard working curve figure in application examples 3;
Figure 13 is the curve map between the initial concentration of Cu (II) in application examples 3 and SH-LNC/MMT adsorbent Cu (II) adsorbance;
Figure 14 is the curve map in application examples 3 between solution ph and SH-LNC/MMT adsorbent Cu (II) adsorbance;
Figure 15 is the curve map in application examples 3 between adsorption temp and SH-LNC/MMT adsorbent Cu (II) adsorbance;
Figure 16 is the curve map in application examples 3 between adsorption time and SH-LNC/MMT adsorbent Cu (II) adsorbance;
Figure 17 is in application examples 3 be 0.04mol/L in solution concentration, and adsorption temp is 20 DEG C, and solution ph is under the condition of 4.0, the pseudo-first-order kinetic model figure of SH-LNC/MMT adsorbent Cu (II);
Figure 18 is in application examples 3 be 0.04mol/L in solution concentration, and adsorption temp is 20 DEG C, and solution ph is under the condition of 4.0, the pseudo-second order kinetic illustraton of model of SH-LNC/MMT adsorbent Cu (II);
Figure 19 is the Langmuir isotherm adsorption model figure of SH-LNC/MMT adsorbent Cu (II) in application examples 3;
Figure 20 is the Freundlich isotherm adsorption model figure of SH-LNC/MMT adsorbent Cu (II) in application examples 3.
Detailed description of the invention
The beneficial effect of implementation process of the present invention and generation will be explained by specific embodiment and Figure of description below, be intended to help reader to understand essence of the present invention and feature better, but not as can the restriction of practical range to this case.
Embodiment 1
Present embodiments provide the preparation method of a kind of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent, wherein, the method comprises the following steps:
(1) preparation of sulfydryl lignocellulosic
53.2000g TGA, 25.9200g acetic anhydride is added in three mouthfuls of round-bottomed flasks, fully mix, place, add 10.0000g lignocellulosic after being cooled to room temperature, take out after 40 DEG C of stirred in water bath 45h, be washed till neutrality with distilled water, suction filtration, be placed in 40 DEG C of baking ovens to dry, grinding obtains yellowish green Powdered sulfydryl lignocellulosic, preserves and is used for carrying out intercalation synthesis reaction with imvite;
(2) preparation of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent
A, sulfydryl lignocellulosic is joined concentration is in batches (sulfydryl lignocellulosic quality: the volume=1:30 of the NaOH aqueous solution in the NaOH aqueous solution of 0.1mol/L, unit is respectively g and mL), stir 40min, form uniform sulfydryl lignocellulosic suspension;
B, the imvite with sulfydryl lignocellulosic equal quality is joined (quality of imvite: the volume=1:30 of distilled water, unit is respectively g and mL) in distilled water, stir 30min, obtain the suspension of imvite;
C, the suspension of imvite is joined in sulfydryl lignocellulosic suspension lentamente, be warming up to 60 DEG C of stirring reaction 8h, centrifugation, neutrality is washed till again with distilled water, after 105 DEG C of vacuum drying 8h, ground 200 mesh sieves, namely can obtain lark pulverous sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent (SH-LNC/MMT).
Embodiment 2
Present embodiments provide the preparation method of a kind of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent, wherein, the method comprises the following steps:
(1) preparation of sulfydryl lignocellulosic
The TGA of 57.4300g, the acetic anhydride of 29.1400g is added in three mouthfuls of round-bottomed flasks, fully mix, place, add the lignocellulosic of 10.0200g after being cooled to room temperature, take out after 43 DEG C of stirred in water bath 47h, be washed till neutrality with distilled water, suction filtration, be placed in 46 DEG C of baking ovens to dry, grinding obtains yellowish green Powdered sulfydryl lignocellulosic, preserves and is used for carrying out intercalation synthesis reaction with imvite;
(2) preparation of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent
A, sulfydryl lignocellulosic is joined concentration is in batches (sulfydryl lignocellulosic quality: the volume=1:37 of the NaOH aqueous solution in the NaOH aqueous solution of 0.18mol/L, unit is respectively g and mL), stir 40min, form uniform sulfydryl lignocellulosic suspension;
B, sulfydryl lignocellulosic and imvite (mass ratio of sulfydryl lignocellulosic and imvite is 1.5:1) are joined (quality of imvite: the volume=1:35 of distilled water in distilled water, unit is respectively g and mL), stir 30min, obtain the suspension of imvite;
C, the suspension of imvite is joined in sulfydryl lignocellulosic suspension lentamente, be warming up to 65 DEG C of stirring reaction 6h, centrifugation, neutrality is washed till again with distilled water, after 110 DEG C of vacuum drying 10h, ground 150 mesh sieves, namely can obtain lark pulverous sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent (SH-LNC/MMT).
Application examples 1
Should provide the application of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent Fe (III) ion in absorption waste water that embodiment 1 prepares by use-case, wherein, this application comprises the following steps:
1, drawing standard working curve
Take iron standard liquid (concentration is 100 μ g/mL) 0.20mL, 0.40mL, 0.60mL, 0.80mL, 1.00mL, 1.20mL respectively, joined respectively again in the volumetric flask of 50mL, be diluted with water to about 20mL, then add the hydroxylamine hydrochloride solution that 2.50mL concentration is 50g/L, shake up.Leave standstill a moment, add the tartaric acid solution that 1.00mL concentration is 50g/L, 5.00mL concentration is 2.5g/L phenanthroline solution, and 10.00mL concentration is the sodium acetate solution of 250g/L, uses distilled water constant volume, shakes up.Then its absorbance is measured with the cuvette of 1mL at 510nm wavelength place.Be abscissa again with concentration, absorbance is ordinate drawing standard working curve, obtains its calibration curve equation, as shown in Figure 1.
2, Fe (III) ion in sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent absorption waste water
Accurately take the SH-LNC/MMT adsorbent of 0.0500g, join in Fe (III) solution of the above-mentioned concentration known of 50mL, be placed in water-bath constant temperature oscillator (120rpm), after reaching adsorption equilibrium under certain condition, centrifugation (rotating speed 6000rpm), get supernatant liquid 5mL, use determined by ultraviolet spectrophotometry absorbance, calculate the residual concentration of Fe (III) in solution.
Under different Fe (III) initial concentration, pH value, adsorption temp and adsorption time, carry out adsorption experiment, calculate sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent (SH-LNC/MMT) to the adsorbance of Fe (III) by formula (1).
In formula (1), Q
1for adsorbance (mg/g); C
0and C
tbe respectively the initial concentration of Fe (III) and the residual concentration (mg/L) of t Fe (III); V is the volume (L) of Fe (III) solution during absorption; M is adsorbent mass (g).
2.1 solution concentrations are on the impact of SH-LNC/MMT adsorbent Fe (III) adsorbance
The initial concentration of Fe (III) on the impact of SH-LNC/MMT adsorbent Fe (III) adsorbance as shown in Figure 2.Adsorption experiment condition is: adsorbent amount is 0.0500g, and pH value is 1.8, and adsorption temp is 40 DEG C, and adsorption time is 40min.As seen from Figure 2, when the initial concentration of Fe (III) is 520-640mg/L, SH-LNC/MMT adsorbent rises very fast to the adsorbance of Fe (III); When concentration is 640-680mg/g, SH-LNC/MMT adsorbent is to slow compared with before 640mg/g of the ascendant trend of the adsorbance of Fe (III), consider in an experiment continue increase concentration time adsorbance also increase thereupon, therefore choose solution concentration be 640mg/g as optium concentration, now maximal absorptive capacity is 631.1300mg/g.This is because along with the increase of Fe (III) concentration, add the contact area of SH-LNC/MMT adsorbent and Fe (III), thus it is very fast that its adsorbance is increased.
2.2pH value is on the impact of SH-LNC/MMT adsorbent Fe (III) adsorbance
Solution ph on the impact of SH-LNC/MMT adsorbent Fe (III) adsorbance as shown in Figure 3.Adsorption experiment condition is: adsorbent amount is 0.0500g, Fe (III) initial concentration solution is 640mg/g, and adsorption temp is 40 DEG C, and adsorption time is 40min.As seen from Figure 3, the pH value of solution increases to the process of 2.47 from 1.71, and before pH=2.0, when pH value is 1.8, the adsorbance of SH-LNC/MMT adsorbent to Fe (III) is maximum, and now adsorbance is 630.9993mg/g; And after pH=1.9, the adsorbance of SH-LNC/MMT adsorbent to Fe (III) is in rising trend, this is due to the increase along with pH value, it is more that Fe (III) precipitates, Fe (III) in solution is reduced, thus the ferrous iron that can develop the color with Phen is reduced, therefore adsorbance is made linearly to increase.Because Fe (III) just starts precipitation when pH=1.9, when pH=3.2, precipitation completely, so choosing optimal pH is 1.8.
2.3 adsorption temps are on the impact of SH-LNC/MMT adsorbance
Adsorption temp on the impact of SH-LNC/MMT adsorbent Fe (III) adsorbance as shown in Figure 4.Adsorption experiment condition is: adsorbent amount is 0.0500g, Fe (III) initial concentration solution is 640mg/g, and solution ph is 1.8, and adsorption time is 40min.As seen from Figure 4, along with the rising of adsorption temp, the adsorbance change of SH-LNC/MMT adsorbent to Fe (III) is irregular, and 40 DEG C time, adsorbance is 630.1502mg/g, and when 45 DEG C, adsorbance declines, and rises again afterwards.In experimentation, at relatively high temperatures, yellow mercury oxide Fe (OH) is had in the conical flask adsorbed
3, may be because high temperature is conducive to Fe (OH) in certain temperature range
3the generation of precipitation, therefore to choose optimal adsorption temperature be 40 DEG C.
2.4 adsorption times are on the impact of SH-LNC/MMT adsorbance
Adsorption time on the impact of SH-LNC/MMT adsorbent Fe (III) adsorbance as shown in Figure 5.Adsorption experiment condition is: adsorbent amount is 0.0500g, Fe (III) initial concentration solution is 640mg/g, and solution ph is 1.8, and adsorption temp is 40 DEG C.As seen from Figure 5, along with the prolongation of adsorption time, the adsorbance of SH-LNC/MMT adsorbent Fe (III) reaches maximal absorptive capacity when 40min, and maximal absorptive capacity is 630.4114mg/g.In adsorption process, along with the prolongation of time, adsorbance is in first increasing rear downward trend, this is because time lengthening is unfavorable for the absorption of adsorbent, therefore at the absorption initial stage, when absorption does not reach saturated, adsorbance increases comparatively obvious, on a declining curve afterwards.So choosing the optimal adsorption time is 40min.
3, adsorption dynamics adsorption kinetics
Adsorption dynamics adsorption kinetics characterizes one of most important characteristics being adsorbed with validity, and good dynamics data correlation can explain heavy metal ion absorption mechanism in the liquid phase well.Under different Fe (III) initial concentration, adsorption time on the impact of SH-LNC/MMT adsorbent Fe (III) adsorbance as shown in Figure 6.Adsorption experiment condition is: adsorbent amount is 0.0500g, and solution ph is 1.8, and adsorption temp is 40 DEG C, and Fe (III) initial concentration solution is respectively 600mg/L, 640mg/L, 680mg/L.
Carry out matching to the curve of adsorption kinetics pseudo-first-order of SH-LNC/MMT adsorbent and accurate pseudo-second-order kinetic equation, wherein, pseudo-first-order and accurate pseudo-second-order kinetic equation are respectively such as formula shown in (2) and formula (3):
In formula (2) and formula (3): Q
efor adsorbance (mgg during adsorption equilibrium
-1); Q
tfor the adsorbance (mgg that adsorption time is t
-1); k
1the First-order equation speed constant that is as the criterion (min
-1); k
2the secondary equation speed constant that is as the criterion (g (mgmin
-1)
-1).
Be 640mg/L in solution concentration, when adsorption temp is 40 DEG C, respectively as shown in Figure 7 and Figure 8, adsorption parameters is as shown in table 1 for the pseudo-first-order kinetic model figure of SH-LNC/MMT adsorbent Fe (III) and pseudo-second order kinetic illustraton of model.As shown in Table 1: the coefficient R of pseudo-first-order kinetic model
2be 0.64417, the coefficient R of pseudo-second order kinetic model
2be 0.9999; k
2much smaller than k
1; The theoretical adsorbance of pseudo-second order kinetic is 628.9308mg/g, than pseudo-first-order theoretical value more close to experiment adsorbance Qe, illustrating that the absorption behavior of SH-LNC/MMT adsorbent to Fe (III) meets pseudo-second order kinetic model thus, take chemisorbed as primary attachment.
Table 1
4, adsorption isotherm
Isothermal adsorption rule is under the condition of temperature constant, and investigate the relation between adsorbance and solution equilibria concentration, its mathematical expression is called adsorption isotherm, and adsorption isotherm is exactly the curve map drawn according to this relation.Fig. 9 is (35 DEG C, 40 DEG C, 45 DEG C) under different adsorption temp, and Fe (III) initial concentration is on the impact of SH-LNC/MMT adsorbent Fe (III) adsorbance.Experiment adsorption conditions is: adsorbent amount is 0.0500g, and solution ph is 1.8, and adsorption time is 40min, and adsorption temp is respectively: 35 DEG C, 40 DEG C, 45 DEG C.
Generally the available Langmuir adsorption isotherm of adsorption equilibrium relation of solute is adsorbed from liquid or gas to solid and Freundlich adsorption isotherm is analyzed experimental data.
Langmuir adsorption isotherm is such as formula shown in (4) and formula (5):
Freundlich adsorption isotherm is such as formula shown in (6):
In formula (4), formula (5) and formula (6): Q
maxfor the maximum adsorption capacity of Langmuir mono layer adsorption, mg/g, this parameter shows that more greatly the adsorption capacity of adsorbent is larger; K
lfor the Langmuir constant relevant with absorption energy; C
ethe concentration of adsorbate in solution when representing adsorption equilibrium, mg/L;
Q
efor adsorbance during liquid equilibrium, mg/g; K
ffor characterizing the Freundlich constant of adsorption capacity; N is adsorption strength index, it is generally acknowledged when Freundlich constant 1/n is 0.1-0.5, easily adsorbs; When 1/n is greater than 2, be difficult to absorption; p
omfor maximum initial mass concentration, mg/L, works as R
lbe preferential absorption time between 0-1.
Be 520mg/L, 600mg/L, 640mg/L, 680mg/L in solution concentration, adsorption time is 40min, adsorption temp is under the condition of 40 DEG C, Langmuir and the Freundlich Isothermal Model figure of adsorbent Fe (III) as shown in Figure 10 and Figure 11.
The isotherm adsorption model relevant parameter of SH-LNC/MMT adsorbent to Fe (III) is as shown in table 2.
Table 2
| Model | Q max(mg/L) | R 2 | b | k f | 1/n |
| Langmuir | 631.1300 | 0.96049 | 1.4947 | ||
| Freundlich | 631.1300 | 0.98907 | 19.6114 | 0.6499 |
As can be seen from Table 2, in Freundlich isotherm formula, 1/n is not within the scope of 0.1-0.5, but it is less than 2, so absorption is not very difficult; The R of Freundlich isotherm formula
2be better than Langmuir, illustrating that the adsorption isotherm of SH-LNC/MMT adsorbent to Fe (III) meets Freundlich isotherm formula, is multi-molecular absorption.
In sum: SH-LNC/MMT adsorbent is larger by the impact of solution ph, initial concentration, adsorption temp and adsorption time on the absorption property of Fe (III).Along with the increase of solution ph, the adsorbance of adsorbent to Fe (III) constantly increases, and reaches optimal adsorption when pH value is 1.8.When solution ph is 1.8, initial concentration is 640mg/L, adsorption temp is 40 DEG C and adsorption time when being 40min, and the maximal absorptive capacity of SH-LNC/MMT adsorbent to Fe (III) is 631.1300mg/g, and this adsorbent has good absorption property to Fe (III).SH-LNC/MMT adsorbent meets pseudo-second order kinetic model and Freundlich isotherm model to Fe (III) adsorption process, sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent (SH-LNC/MMT) adsorbent is described to the absorption of Fe (III) based on chemisorbed and be multi-molecular absorption.
Application examples 2
Should provide the application of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent Fe (III) ion in absorption waste water that embodiment 1 prepares by use-case, wherein, this application comprises the following steps:
Should experimental implementation in use-case with application examples 1, just experiment condition parameter slightly changes.
Should the adsorption experiment condition of use-case be: adsorbent amount is 0.0500g, Fe (III) initial concentration solution is 1280mg/g, solution ph is 2.1, adsorption temp is 70 DEG C, adsorption time is 80min, and the maximal absorptive capacity of the SH-LNC/MMT adsorbent obtained thus to Fe (III) is 596.87mg/g.
Comparative example 1
This comparative example provides the application of lignocellulosic/montmorillonite Composite heavy metal (LNC/MMT) adsorbent Fe (III) ion in absorption waste water, and wherein, this application comprises the following steps:
Experimental implementation in this comparative example is with application examples 1, and just experiment condition parameter slightly changes.The adsorption experiment condition of this comparative example is: adsorbent amount is 0.0500g, Fe (III) initial concentration solution is 640mg/g, solution ph is 1.8, adsorption temp is 40 DEG C, adsorption time is 40min, and the maximal absorptive capacity of the LNC/MMT adsorbent obtained thus to Fe (III) is 271.12mg/g.And the maximal absorptive capacity of the SH-LNC/MMT adsorbent obtained in application examples 1 to Fe (III) is 631.13mg/g, adsorption experiment condition is: adsorbent amount is 0.0500g, Fe (III) initial concentration solution is 640mg/g, solution ph is 1.8, adsorption temp is 40 DEG C, and adsorption time is 40min.This shows, sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent provided by the invention to the maximal absorptive capacity (631.13mg/g) of Fe (III) far above the maximal absorptive capacity (271.12mg/g) without sulfhydryl modified LNC/MMT adsorbent.
Comparative example 2
This comparative example provides the application of lignocellulosic/montmorillonite Composite heavy metal (LNC/MMT) adsorbent Fe (III) ion in absorption waste water, and wherein, this application comprises the following steps:
Experimental implementation in this comparative example is with application examples 1, and just experiment condition parameter slightly changes.The adsorption experiment condition of this comparative example is: adsorbent amount is 0.0500g, Fe (III) initial concentration solution is 1280mg/g, solution ph is 2.1, adsorption temp is 70 DEG C, adsorption time is 80min, and the maximal absorptive capacity of the LNC/MMT adsorbent obtained thus to Fe (III) is 452.06mg/g.And the maximal absorptive capacity of the SH-LNC/MMT adsorbent obtained in application examples 2 to Fe (III) is 596.87mg/g, adsorption experiment condition is: adsorbent amount is 0.0500g, Fe (III) initial concentration solution is 1280mg/g, solution ph is 2.1, adsorption temp is 70 DEG C, and adsorption time is 80min.This shows, sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent provided by the invention to the maximal absorptive capacity (596.87mg/g) of Fe (III) higher than the maximal absorptive capacity (452.06mg/g) without sulfhydryl modified LNC/MMT adsorbent.
Application examples 3
Should provide the application of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent Cu (II) ion in absorption waste water that embodiment 1 prepares by use-case, wherein, this application comprises the following steps:
1, drawing standard working curve
Cu (II) standard liquid (concentration is 10ug/mL) of 1.0mL, 1.2mL, 1.4mL, 1.6mL, 2.0mL is accurately added in 50mL volumetric flask, the citric acid solution of 2mL, the ammonia spirit of 4mL, bisoxalydihydrazone (BCO) solution of 10mL, shake up, be diluted to scale.After 10min, (instrument preheating 10min) is with 610nm wavelength, and 3cm cuvette distilled water is blank reference, measures absorbance, be abscissa again with concentration, absorbance is ordinate drawing standard working curve, obtains its calibration curve equation, as shown in figure 12.
2, Cu (II) ion in sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent absorption waste water
Accurately take the SH-LNC/MMT adsorbent of 0.0500g, join in Cu (II) solution of 50mL concentration known, be placed in water-bath constant temperature oscillator (120rpm), after reaching adsorption equilibrium under certain condition, centrifugation (rotating speed 6000rpm), get supernatant liquid 5mL, then adopt determined by ultraviolet spectrophotometry absorbance, calculate the residual concentration of Cu (II) in solution.
Under different Cu (II) initial concentration, pH value, adsorption temp and adsorption time, carry out adsorption experiment, calculate SH-LNC/MMT adsorbent to the adsorbance of Cu (II) by formula (7).
In formula (7), Q is adsorbance (mg/g); C
0and C
tbe respectively the initial concentration of Cu (II) and the residual concentration (mol/L) of t Cu (II); V is the volume (L) of Cu (II) solution during absorption; M is adsorbent mass (g).
2.1 solution concentrations are on the impact of SH-LNC/MMT adsorbent Cu (II) adsorbance
The initial concentration of Cu (II) on the impact of SH-LNC/MMT adsorbent Cu (II) adsorbance as shown in figure 13.Adsorption experiment condition is: adsorbent amount is 0.0500g, and pH value is 4.0, and adsorption temp is 20 DEG C, and adsorption time is 60min.As seen from Figure 13, along with the increase of Cu (II) initial concentration solution, SH-LNC/MMT adsorbent increases the adsorbance of copper ion.When the concentration of Cu (II) is 0.04mol/L, substantially tend to balance, adsorbance is 342.56mg/g.Subsequently, along with the continuation of copper ion concentration increases, adsorbance tend towards stability in more among a small circle fluctuate.Therefore determine that optimal adsorption concentration is 0.04mol/L.
2.2pH value is on the impact of SH-LNC/MMT adsorbent Cu (II) adsorbance
Solution ph on the impact of SH-LNC/MMT adsorbent Cu (II) adsorbance as shown in figure 14.Adsorption experiment condition is: adsorbent amount is 0.0500g, Cu (II) initial concentration solution is 0.04mol/L, and adsorption temp is 20 DEG C, and adsorption time is 60min.As seen from Figure 14, when pH value is greater than 3.0, along with the increase of liquid phase PH valve, adsorbent slowly increases in a certain scope (pH value is 3.0-4.0) the adsorbance of copper ion.Its main cause be absorption saturated, also have partly cause be because imvite surface dissociable go out comparatively polyhydroxy, make adsorbent surface positive charge intensive, same sex electric charge repels the further absorption that have impact on adsorbent mutually; But when continuing to increase acidity, adsorbance can rise to some extent, and this mainly because under the environment that pH value is larger, has started the precipitation occurring Cu (II).Can determine thus, the optimal pH scope of adsorption process is about 4.0.
2.3 adsorption temps are on the impact of SH-LNC/MMT adsorbance
Adsorption temp on the impact of SH-LNC/MMT adsorbent Cu (II) adsorbance as shown in figure 15.Adsorption experiment condition is: adsorbent amount is 0.0500g, Cu (II) initial concentration solution is 0.04mol/L, and solution ph is 4.0, and adsorption time is 60min.As seen from Figure 15, temperature is raised to the process of 80 DEG C from 10 DEG C, the process that the ability of SH-LNC/MMT adsorbent copper ion declines after presenting and first raising gradually, illustrate that the adsorption process of adsorbent to copper ion is one and increases with temperature, the system degree of disorder reduce exothermic process, as can be seen here this adsorbent to the absorption of copper ion based on chemisorbed.Therefore to choose optimum temperature be 20 DEG C.
2.4 adsorption times are on the impact of SH-LNC/MMT adsorbance
Adsorption time on the impact of SH-LNC/MMT adsorbent Cu (II) adsorbance as shown in figure 16.Adsorption experiment condition is: adsorbent amount is 0.0500g, Cu (II) initial concentration solution is 0.04mol/L, and solution ph is 4.0, and adsorption temp is 20 DEG C.As seen from Figure 16, time when reacted within 60min, the adsorbance of adsorbent to Cu (II) is on the rise with the prolongation of adsorption time, when adsorption time reaches 60min, adsorbance reaches maximum, substantially keep homeostasis afterwards, whole adsorption process adsorbance extends in time in first increasing the trend tended to balance afterwards.Therefore the optimal adsorption time is selected to be 60min.
3, adsorption dynamics adsorption kinetics
When carrying out data processing to adsorption dynamics adsorption kinetics, the optimum condition selected is: concentration is 0.04mol/L, and adsorption temp is 20 DEG C, and solution ph is 4.0.Linear regression fit is carried out to the curve of adsorption kinetics pseudo-first-order of SH-LNC/MMT adsorbent and accurate pseudo-second-order kinetic equation: wherein, pseudo-first-order and accurate pseudo-second-order kinetic equation are respectively such as formula shown in (8), formula (9):
In formula (8), formula (9): q
efor adsorbance (mgg during adsorption equilibrium
-1); q
tfor the adsorbance (mgg that adsorption time is t
-1); k
1the First-order equation speed constant that is as the criterion (min
-1); k
2the secondary equation speed constant that is as the criterion (g (mgmin
-1)
-1).
Be 0.04mol/L in solution concentration, adsorption temp is 20 DEG C, and when solution ph is 4.0, the one-level of SH-LNC/MMT adsorbent Cu (II), second-order kinetics illustraton of model are respectively as shown in Figure 17, Figure 18.From Figure 17, Figure 18, the adsorption dynamics adsorption kinetics of SH-LNC/MMT adsorbent does not meet pseudo-first-order kinetic model, but meets pseudo-second order kinetic model, coefficient R
2=0.9929.Therefore, the absorption of SH-LNC/MMT to Cu (II) meets accurate secondary absorption rate equation, based on chemisorbed.
4, adsorption isotherm
Isothermal adsorption rule is under the condition of temperature constant, and investigate the relation between adsorbance and solution equilibria concentration, its mathematical expression is called adsorption isotherm, and adsorption isotherm is exactly the curve map drawn according to this relation.The adsorption equilibrium of generally adsorbing solute to solid from liquid or gas closes available Langmuir adsorption isotherm and Freundlich adsorption isotherm is analyzed experimental data.Use and calculate as shown in the formula (10) and formula (11):
Formula (10) is with in formula (11): b is the Langmuir constant (Lmg relevant with absorption energy
-1); N, K
ffor Freundlich constant; C
efor remaining the concentration of Cu (II) in solution during adsorption equilibrium, (molL
-1); q
maxfor single molecular layer saturated absorption (mgg
-1); q
efor the equilibrium adsorption capacity (mgg of Cu (II)
-1).
Langmuir and the Freundlich Isothermal Model figure of adsorbent Cu (II) as illustrated in figures 19 and 20.
From the fitting result of Figure 19 and Figure 20, the absorption of SH-LNC/MMT adsorbent to Cu (II) more meets Langmuir isotherm adsorption model.Linearly dependent coefficient R
2=0.9465, illustrate that this adsorption process belongs to mono layer adsorption.
In sum: at employing SH-LNC/MMT adsorbent in the adsorption process of Cu (II), this adsorbent is that the adsorption effect of the Cu (II) of 0.04mol/L is best to concentration, and its optimal adsorption temperature is 20 DEG C, close to room temperature, this is the condition being easy to meet to the absorption of industrial wastewater, can reduce cost absorption.The optimal adsorption time of this adsorbent to Cu (II) is a hours, and extend adsorption time, adsorbance has downward trend on the contrary in certain interval.And the impact of acidity on this process is mainly manifested in, when acidity is less, sulfydryl can not realize good absorption because of inactivation; When acidity is larger, copper ion can start again to precipitate causes the mensuration of adsorbance to be affected.Therefore, optimal adsorption condition is the initial concentration of Cu (II) is 0.04mol/L, and pH value is 4.0, and adsorption temp is 20 DEG C, and adsorption time is 60min, and the maximal absorptive capacity now obtained is 342.56mg/g.Kinetics model of biosorption meets pseudo-second order kinetic model, and adsorption isotherm meets Langmuir model.
Application examples 4
Should provide the application of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent Cu (II) ion in absorption waste water that embodiment 1 prepares by use-case, wherein, this application comprises the following steps:
Should experimental implementation in use-case with application examples 3, just experiment parameter slightly changes.Should the adsorption experiment condition of use-case be: SH-LNC/MMT adsorbent amount is 0.0500g, Cu (II) initial concentration solution is 0.03mol/L, solution ph is 4.9, adsorption temp is 50 DEG C, adsorption time is the maximal absorptive capacity of 60min, SH-LNC/MMT adsorbent to Cu (II) is 338.16mg/g.
Comparative example 3
This comparative example provides the application of lignocellulosic/montmorillonite Composite heavy metal (LNC/MMT) adsorbent Cu (II) ion in absorption waste water, and wherein, this application comprises the following steps:
Experimental implementation in this comparative example is with application examples 3, and just experiment parameter slightly changes.The adsorption experiment condition of this comparative example is: adsorbent amount is 0.0500g, Cu (II) initial concentration solution is 0.04mol/L, solution ph is 4.0, adsorption temp is 20 DEG C, adsorption time is 60min, and the maximal absorptive capacity of the LNC/MMT adsorbent obtained thus to Cu (II) is 196.25mg/g.And the maximal absorptive capacity of the SH-LNC/MMT adsorbent obtained in application examples 3 to Cu (II) is 342.56mg/g, adsorption experiment condition is: adsorbent amount is 0.0500g, the initial concentration of Cu (II) is 0.04mol/L, pH value is 4.0, adsorption temp is 20 DEG C, and adsorption time is 60min.This shows, sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent provided by the invention to the maximal absorptive capacity (342.56mg/g) of Cu (II) higher than the maximal absorptive capacity (196.25mg/g) without sulfhydryl modified LNC/MMT adsorbent.
Comparative example 4
This comparative example provides the application of lignocellulosic/montmorillonite Composite heavy metal (LNC/MMT) adsorbent Cu (II) ion in absorption waste water, and wherein, this application comprises the following steps:
Experimental implementation in this comparative example is with application examples 3, and just experiment parameter slightly changes.The adsorption experiment condition of this comparative example is: adsorbent amount is 0.0500g, Cu (II) initial concentration solution is 0.03mol/L, solution ph is 4.9, adsorption temp is 50 DEG C, adsorption time is 60min, and the maximal absorptive capacity of the LNC/MMT adsorbent obtained thus to Cu (II) is 322.56mg/g.And the maximal absorptive capacity of the SH-LNC/MMT adsorbent obtained in application examples 4 to Cu (II) is 338.16mg/g, adsorption experiment condition is: SH-LNC/MMT adsorbent amount is 0.0500g, Cu (II) initial concentration solution is 0.03mol/L, solution ph is 4.9, adsorption temp is 50 DEG C, and adsorption time is 60min.This shows, sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent provided by the invention to the maximal absorptive capacity (338.16mg/g) of Cu (II) higher than the maximal absorptive capacity (322.56mg/g) without sulfhydryl modified LNC/MMT adsorbent.
Claims (10)
1. sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent, wherein, this adsorbent is formed by sulfydryl lignocellulosic and montmorillonite Composite;
The mass ratio of described sulfydryl lignocellulosic and imvite is 1:1-1.5:1; Described sulfydryl lignocellulosic intercalation enters between the lamella of described imvite;
The granularity of preferred described sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent is 150-200 order.
2. the preparation method of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent according to claim 1, wherein, the method comprises the following steps:
A, sulfydryl lignocellulosic is added in sodium hydrate aqueous solution, obtain the suspension of sulfydryl lignocellulosic; The concentration of preferred described sodium hydrate aqueous solution is 0.1-0.2mol/L;
B, imvite to be added to the water, to obtain the suspension of imvite;
C, added by the suspension of described imvite in the suspension of sulfydryl lignocellulosic, heating makes it react, and by product washing to neutral, after drying, obtains described sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent.
3. preparation method according to claim 2, wherein, the ratio of the quality of the lignocellulosic of sulfydryl described in step a and the volume of sodium hydrate aqueous solution is 1:30-1:35, and unit is respectively g and mL.
4. preparation method according to claim 2, wherein, the mass ratio of the lignocellulosic of sulfydryl described in step b and imvite is 1:1-1.5:1; The ratio of the quality of imvite described in step b and the volume of water is 1:30-1:40, and unit is respectively g and mL.
5. preparation method according to claim 2, wherein, the temperature adding thermal response described in step c is 60-65 DEG C, and the reaction time is 6-8h.
6. preparation method according to claim 2, wherein, drying described in step c is 100-110 DEG C of dry 8-10h.
7. the preparation method according to any one of claim 2-6, wherein, the preparation method of described sulfydryl lignocellulosic comprises the following steps:
TGA and acetic anhydride are mixed, after cooling, adds lignocellulosic, react under water-bath, then by product washing to neutral post-drying, obtain described sulfydryl lignocellulosic;
The mass ratio of described TGA, acetic anhydride, lignocellulosic is 5-6:2-3:1;
Be cooled to preferably and be cooled to room temperature.
8. preparation method according to claim 7, wherein, the temperature of described water-bath is 40-45 DEG C, and the reaction time is 45-48h.
9. preparation method according to claim 7, wherein, the temperature of described oven dry is 40-50 DEG C.
10. sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent according to claim 1 is removing the application in heavy metal contained by waste water.
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