CN105107471B - Sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent and preparation and application - Google Patents

Sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent and preparation and application Download PDF

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CN105107471B
CN105107471B CN201510583535.0A CN201510583535A CN105107471B CN 105107471 B CN105107471 B CN 105107471B CN 201510583535 A CN201510583535 A CN 201510583535A CN 105107471 B CN105107471 B CN 105107471B
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lignocellulosic
sulfydryl
montmorillonite
heavy metal
adsorption
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CN201510583535.0A
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CN105107471A (en
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张晓涛
王喜明
刘建霞
李蜀眉
姬宇飞
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内蒙古农业大学
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Abstract

The invention provides a kind of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent and preparation and application.The adsorbent is formed by sulfydryl lignocellulosic with montmorillonite Composite;The sulfydryl lignocellulosic and the mass ratio of montmorillonite are 1:1‑1.5:1;The sulfydryl lignocellulosic intercalation enters between the lamella of the montmorillonite.Application present invention also offers the preparation method of above-mentioned sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent and its in heavy metal contained by removing waste water.The preparation method of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent of the present invention, which has, to be prepared simple, raw material and is easy to get and environmentally friendly, not the features such as not causing secondary pollution, obtained sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent is nontoxic, biodegradable and cost is cheap, use it for removing the heavy metal ion contained in waste water, the adsorption operations of the adsorbent are easy, and adsorbance is high.

Description

Sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent and preparation and application
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 in China, water resource quality also constantly decline.Due to from ore processing, process hides, plating and face A large amount of discharges of all types of industries waste water of industry such as material, wherein many heavy metal ion enter in water, air and soil, and with each Kind chemical form is retained, accumulates and migrated, and this causes huge harm to human environment, the ecological disruption thereby resulted in and warp Ji loss is also immeasurable.So the improvement of industrial wastewater has caused the concern of whole world various countries.
In recent years, Inner Mongolia, such as Chifeng City, Ordos City, packet header and hold in the palm the mining on county ground, plating, metallurgy, The industry such as pharmacy enters the period of rapid growth.In people's living environment, the washes containing various heavy metal ion, plating A large amount of industrial pollutants such as waste water gradually increase, and the economic value of these industrial wastewaters is higher, but the health of the Ye Duiwo areas people Serious harm is generated with living environment, my district government also implements corresponding policies and regulations to protect water source, pre- waterproof Body pollution.Nowadays, people propose higher requirement to health, environmental protection, sustainable development etc., thus driven it is green, The repeatable Industrial Wastewater Treatment new material new technological industry rapid growth utilized.
Traditional heavy metal industrial effluent processing method mainly have chemical precipitation method, ion-exchange, electrochemical treatment, Membrane technology etc., these processing methods achieve good effect to a certain extent, but generally existing is expensive, settling property It is poor, seriously polluted, service life is short, the shortcomings of being not easy to regenerate, these shortcomings are very restricted its practical application.And inhale Attached method has been to be concerned by more and more people as a kind of new heavy metals removal, recovery technology.Absorption method is mainly using cheap Biomaterial heavy metal adsorbed, the low-concentration heavy metal industrial wastewater that is particularly suitable for use in (<Processing 100mg/L), this The new Absorbent of inexpensive, efficient, nontoxic, reusable edible the biomass degradation material comprehensive utilization of class, which has, to be inhaled The advantages that attached efficiency high and fast adsorption rate, paid attention to extensively.
So far, both at home and abroad to biodegradable polymer (such as:Starch, pine nut powder, cellulose, glycan, chitosan, Cellulose and lignin) and its research of derivative and inorganic clay nano-complex primarily focus on structure and material property, Most of research on degradable natural high molecular polymer/inorganic clay nanocomposites lays particular emphasis on mechanics, thermodynamics It is less to the report of heavy metals in industrial wastewater ionic adsorption and desorption performance with the aspect of performance such as gas barrier, and do not have The theory of formation system carrys out Instructing manufacture practice.Prior art is for lignocellulosic and montmorillonite (LNC/MMT) and its and calcium The preparation of based montmorillonite nanometer composite material and adsorption-desorption to heavy metal ions in wastewater and dyestuff, which have been done, largely to be ground Study carefully work, but on studying the system for the lignocellulosic/Nano composite material of montmorillonite adsorbent being modified containing activity functional groups Heavy metal ion in standby and its absorption and desorption industrial wastewater has not been reported.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of sulfydryl lignocellulosic/montmorillonite Composite Heavy metal absorbent.
The present invention also aims to provide a kind of above-mentioned sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent Preparation method.
The present invention also aims to provide a kind of above-mentioned sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent to exist Remove the application in heavy metal contained by waste water.
For the above-mentioned purpose, should the invention provides a kind of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent Adsorbent is formed by sulfydryl lignocellulosic with montmorillonite Composite;
The sulfydryl lignocellulosic and the mass ratio of montmorillonite are 1:1-1.5:1;It is preferred that sulfydryl lignocellulosic is with covering The mass ratio for taking off soil is 1:1;
The sulfydryl lignocellulosic intercalation enters between the lamella of the montmorillonite.
According to the preferred embodiment of the present invention, the sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent Granularity is 150-200 mesh.
, should present invention also offers the preparation method of above-mentioned sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent Sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent is prepared by solution in-situ intercalated polymerization, should Method comprises the following steps:
A, sulfydryl lignocellulosic is added in sodium hydrate aqueous solution, obtains the suspension of sulfydryl lignocellulosic;
B, montmorillonite is added to the water, obtains the suspension of montmorillonite;
C, the suspension of the montmorillonite is added in the suspension of sulfydryl lignocellulosic, heating makes its reaction, will Reaction product is washed to neutrality, after drying, obtains the sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent.
According to the preferred embodiment of the present invention, by sulfydryl lignocellulosic by the way of " being added portionwise " in step a It is added in sodium hydrate aqueous solution, the purpose " being added portionwise " herein is in order that sulfydryl lignocellulosic can preferably dissolve In alkali lye, and disposably add, need stirring for a long time, experimental implementation can waste time and energy, and be more convenient for so operation is added portionwise The progress of experiment.The present invention does not have specific requirement, people in the art to the charging times of " being added portionwise " and each feeding quantity Member can need to select suitable charging times and each addition to be fed 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 quality of sulfydryl lignocellulosic described in step a and sodium hydroxide water The ratio of the volume of solution is 1:30-1:35, unit is respectively g and mL;It is preferred that the quality and hydrogen of the sulfydryl lignocellulosic The ratio of the volume of aqueous solution of sodium oxide is 1:30, unit is respectively g and mL.
According to the preferred embodiment of the present invention, sulfydryl lignocellulosic described in step b and the mass ratio of montmorillonite are 1:1-1.5:1, preferably 1:1;The ratio of the quality of montmorillonite and the volume of water described in step b is 1:30-1:40, be preferably 1:30, unit is respectively g and mL.
According to the preferred embodiment of the present invention, the temperature of heating response described in step c is 60-65 DEG C, the reaction time For 6-8h;It is preferred that the temperature of the heating response is 60 DEG C, reaction time 8h.
According to the preferred embodiment of the present invention, drying is 100-110 DEG C of dry 8-10h described in step c;It is it is preferred that described Drying is 105 DEG C of dry 8h.
According to the preferred embodiment of the present invention, the sulfydryl lignocellulosic is by TGA and lignocellulosic Obtained from part esterification occurs for alcoholic extract hydroxyl group, its specific preparation method is as follows:
TGA and acetic anhydride are well mixed, after cooling, lignocellulosic is added, is reacted under water-bath, then will reaction Product is dried after washing to neutrality, obtains the sulfydryl lignocellulosic.
It is described to be cooled to cool down in the preparation process of sulfydryl lignocellulosic according to the preferred embodiment of the present invention To room temperature.
According to the preferred embodiment of the present invention, in the preparation process of sulfydryl lignocellulosic, the temperature of the water-bath For 40-45 DEG C, reaction time 45-48h;
It is preferred that the temperature of the water-bath is 40 DEG C, reaction time 45h.
According to the preferred embodiment of the present invention, in the preparation process of sulfydryl lignocellulosic, the temperature of the drying For 40-50 DEG C, the temperature of preferably described drying is 40 DEG C.
Present invention also offers above-mentioned sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent contained by removing waste water Application in heavy metal.
The preparation method of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent of the present invention is with Inner Mongolia Autonomous Region Abundant lignocellulosic (LNC) and montmorillonite (MMT) is raw material, is made by carrying out thiol chemistry modification to lignocellulosic Sulfydryl lignocellulosic (SH-LNC), then SH-LNC and MMT (it has nanoscale lamellar structure) progress is in-situ inserted compound Reaction, sulfydryl lignocellulosic intercalation enter in the nanoscale lamellar structure of montmorillonite, and sulfydryl wood fibre is prepared first Element/montmorillonite (SH-LNC/MMT) nano composite material, i.e. sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent.This The preparation method of invention realizes the combination of sulfydryl lignocellulosic and montmorillonite on nanoscale, makes hydrophilic clay Mineral surfaces hydrophobization, while pass through the surface energy that organic-treating also reduces clay mineral, enhance lamella and polymer Compatibility between strand, improve between mineral and polymer boundary moisture effect, further increase inorganic phase with Interface affinity between organic phase;In addition, the presence of sulfydryl is advantageously mutual between lignocellulosic and montmorillonite With reference to its presence can also promote the solubility of montmorillonite, weaken the suspending power of montmorillonite in the solution, allow its more preferable Ground is dissolved in solution and can preferably adsorb heavy metal ion.
The preparation method of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent of the present invention is with Inner Mongolia Autonomous Region Abundant lignocellulosic (LNC) and montmorillonite (MMT) is raw material, wherein, LNC is widely present in nature, and with biology Degradability, and MMT is in Inner Mongolia Autonomous Region rich reserves, A wide selection of colours and designs and cheap.
In addition, the preparation method of the present invention is easy to get with simple, raw material is prepared, and it is environmentally friendly, secondary dirt is not caused The features such as dye, there is huge economic and social benefit.
Sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent of the invention is nontoxic, biodegradable and cost is low Honest and clean, the adsorbent has between chelation group (- SH), activity functional groups and montmorillonite layer on LNC molecular skeletons simultaneously Isomorphous substitution phenomenon, the adsorption effect something which increases the adsorbent to heavy metal ions in wastewater.
Sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent of the present invention is used to remove the weight contained in waste water Metal ion, the adsorption operations of the adsorbent are easy, and adsorbance is high.
Brief description of the drawings
Fig. 1 is the standard working curve figure in application examples 1;
Fig. 2 is between the initial concentration and SH-LNC/MMT adsorbents Fe (III) adsorbance of Fe (III) in application examples 1 Curve map;
Fig. 3 is the curve map between solution ph and SH-LNC/MMT adsorbents Fe (III) adsorbance in application examples 1;
Fig. 4 is the curve map between adsorption temp and SH-LNC/MMT adsorbents Fe (III) adsorbance in application examples 1;
Fig. 5 is the curve map between adsorption time and SH-LNC/MMT adsorbents Fe (III) adsorbance in application examples 1;
Fig. 6 is adsorption time and SH-LNC/MMT adsorbents Fe (III) in application examples 1 under different Fe (III) initial concentrations Curve map between adsorbance;
Fig. 7 is to be 640mg/L in solution concentration in application examples 1, and when adsorption temp is 40 DEG C, SH-LNC/MMT adsorbents are inhaled The pseudo-first-order kinetic model figure of attached Fe (III);
Fig. 8 is to be 640mg/L in solution concentration in application examples 1, and when adsorption temp is 40 DEG C, SH-LNC/MMT adsorbents are inhaled The pseudo-second order kinetic illustraton of model of attached Fe (III);
Fig. 9 is Fe (III) initial concentrations and SH-LNC/ in application examples 1 under different adsorption temps (35 DEG C, 40 DEG C, 45 DEG C) Curve map between MMT adsorbents Fe (III) adsorbance;
It in application examples 1 in solution concentration is 520mg/L, 560mg/L, 600mg/L, 640mg/L, 680mg/L that Figure 10, which is, is inhaled The attached time is 40min, under conditions of adsorption temp is 40 DEG C, SH-LNC/MMT adsorbents absorption Fe (III) Langmuir etc. Warm Adsorption Model figure;
It in application examples 1 in solution concentration is 520mg/L, 560mg/L, 600mg/L, 640mg/L, 680mg/L that Figure 11, which is, is inhaled The attached time is 40min, under conditions of adsorption temp is 40 DEG C, SH-LNC/MMT adsorbents absorption Fe (III) Freundlich Isotherm adsorption model figure;
Figure 12 is the standard working curve figure in application examples 3;
Figure 13 is the song between Cu (II) initial concentration and SH-LNC/MMT adsorbents Cu (II) adsorbance in application examples 3 Line chart;
Figure 14 is the curve map between solution ph and SH-LNC/MMT adsorbents Cu (II) adsorbance in application examples 3;
Figure 15 is the curve map between adsorption temp and SH-LNC/MMT adsorbents Cu (II) adsorbance in application examples 3;
Figure 16 is the curve map between adsorption time and SH-LNC/MMT adsorbents Cu (II) adsorbance in application examples 3;
It in application examples 3 in solution concentration is 0.04mol/L that Figure 17, which is, and adsorption temp is 20 DEG C, and solution ph is 4.0 bar Under part, the pseudo-first-order kinetic model figure of SH-LNC/MMT adsorbents Adsorption of Cu (II);
It in application examples 3 in solution concentration is 0.04mol/L that Figure 18, which is, and adsorption temp is 20 DEG C, and solution ph is 4.0 bar Under part, the pseudo-second order kinetic illustraton of model of SH-LNC/MMT adsorbents Adsorption of Cu (II);
Figure 19 is the Langmuir isotherm adsorption model figures of SH-LNC/MMT adsorbents Adsorption of Cu (II) in application examples 3;
Figure 20 is the Freundlich isotherm adsorption model figures of SH-LNC/MMT adsorbents Adsorption of Cu (II) in application examples 3.
Embodiment
The implementation process and caused of the present invention will be explained by specific embodiment and Figure of description below Beneficial effect, it is intended to help reader to more fully understand the essence and feature of the present invention, but can implement model not as to this case The restriction enclosed.
Embodiment 1
A kind of preparation method of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent is present embodiments provided, its In, this method comprises the following steps:
(1) preparation of sulfydryl lignocellulosic
53.2000g TGAs, 25.9200g acetic anhydrides are added in three neck round bottom flask, is sufficiently mixed uniformly, puts Put, add 10.0000g lignocellulosics after being cooled to room temperature, take out after 40 DEG C of stirred in water bath 45h, be washed to distillation Neutrality, filter, be placed in 40 DEG C of baking ovens and dry, grinding obtain the powdered sulfydryl lignocellulosic of yellow green, preserve for Montmorillonite carries out intercalation synthesis reaction;
(2) preparation of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent
A, sulfydryl lignocellulosic is added to (the wooden fibre of sulfydryl in the NaOH aqueous solution that concentration is 0.1mol/L in batches Tie up quality amount:Volume=1 of the NaOH aqueous solution:30, unit is respectively g and mL), 40min is stirred, it is wooden to form uniform sulfydryl Cellulose suspension;
B, the montmorillonite with sulfydryl lignocellulosic equal quality is added in distilled water (the quality of montmorillonite:Distillation Volume=1 of water:30, unit is respectively g and mL), 30min is stirred, obtains the suspension of montmorillonite;
C, the suspension of montmorillonite is slowly added into sulfydryl lignocellulosic suspension, it is anti-is warming up to 60 DEG C of stirrings 8h is answered, is centrifuged, then neutrality is washed to distillation, after 105 DEG C are dried in vacuo 8h, ground 200 mesh sieve, you can to obtain The powdered sulfydryl lignocellulosic of lark/montmorillonite Composite heavy metal absorbent (SH-LNC/MMT).
Embodiment 2
A kind of preparation method of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent is present embodiments provided, its In, this method comprises the following steps:
(1) preparation of sulfydryl lignocellulosic
57.4300g TGA, 29.1400g acetic anhydride is added in three neck round bottom flask, is sufficiently mixed uniformly, Place, be cooled to the lignocellulosic of addition 10.0200g after room temperature, taken out after 43 DEG C of stirred in water bath 47h, use distilled water Neutrality is washed till, is filtered, is placed in 46 DEG C of baking ovens and dries, grinding obtains the powdered sulfydryl lignocellulosic of yellow green, preserves and uses In with montmorillonite carry out intercalation synthesis reaction;
(2) preparation of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent
A, sulfydryl lignocellulosic is added to concentration as (sulfydryl is wooden in the 0.18mol/L NaOH aqueous solution in batches Cellulose quality:Volume=1 of the NaOH aqueous solution:37, unit is respectively g and mL), 40min is stirred, forms uniform sulfydryl wood Matter cellulose suspension;
B, by sulfydryl lignocellulosic and montmorillonite, (sulfydryl lignocellulosic and the mass ratio of montmorillonite are 1.5:1) add (the quality of montmorillonite into distilled water:Volume=1 of distilled water:35, unit is respectively g and mL), 30min is stirred, is covered Take off the suspension of soil;
C, the suspension of montmorillonite is slowly added into sulfydryl lignocellulosic suspension, it is anti-is warming up to 65 DEG C of stirrings 6h is answered, is centrifuged, then neutrality is washed to distillation, after 110 DEG C are dried in vacuo 10h, ground 150 mesh sieve, you can to obtain The powdered sulfydryl lignocellulosic of lark/montmorillonite Composite heavy metal absorbent (SH-LNC/MMT).
Application examples 1
The application example provides sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent that embodiment 1 is prepared The application of Fe (III) ion in waste water is adsorbed, wherein, the application comprises the following steps:
1st, standard working curve is drawn
Weigh respectively iron standard liquid (concentration is 100 μ g/mL) 0.20mL, 0.40mL, 0.60mL, 0.80mL, 1.00mL, 1.20mL, then add it to respectively in 50mL volumetric flask, 20mL or so is diluted with water to, then adding 2.50mL concentration is 50g/L hydroxylamine hydrochloride solution, shakes up.A moment is stood, adds the tartaric acid solution that 1.00mL concentration is 50g/L, 5.00mL is dense It is 250g/L sodium acetate solution to spend for 2.5g/L phenanthroline solution, 10.00mL concentration, with distilled water constant volume, is shaken up.So Its absorbance is measured at 510nm wavelength with 1mL cuvette afterwards.Again using concentration as abscissa, absorbance is drawn for ordinate Standard working curve, its calibration curve equation is obtained, as shown in Figure 1.
2nd, Fe (III) ion in sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent absorption waste water
The accurate SH-LNC/MMT adsorbents for weighing 0.0500g, it is added to Fe (III) solution of the above-mentioned concentration knowns of 50mL In, it is placed in water-bath constant temperature oscillator (120rpm), after reaching adsorption equilibrium under certain condition, centrifuges (rotating speed 6000rpm), supernatant liquid 5mL is taken, using determined by ultraviolet spectrophotometry absorbance, calculates the residue of Fe (III) in solution Concentration.
Adsorption experiment is carried out under different Fe (III) initial concentration, pH value, adsorption temp and adsorption time, by formula (1) Calculate adsorbance of the sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent (SH-LNC/MMT) to Fe (III).
In formula (1), Q1For adsorbance (mg/g);C0And CtRespectively Fe (III) initial concentration and t Fe's (III) Residual concentration (mg/L);The volume (L) of Fe (III) solution when V is absorption;M is adsorbent mass (g).
Influence of 2.1 solution concentrations to SH-LNC/MMT adsorbents Fe (III) adsorbance
Influence of Fe (III) initial concentration to SH-LNC/MMT adsorbents Fe (III) adsorbance is as shown in Figure 2.Absorption Experiment condition is:Adsorbent amount is 0.0500g, and pH value 1.8, adsorption temp is 40 DEG C, adsorption time 40min.By Fig. 2 As can be seen that when Fe (III) initial concentration is 520-640mg/L, SH-LNC/MMT adsorbents are in Fe (III) adsorbance Rise very fast;When concentration is 640-680mg/g, SH-LNC/MMT adsorbents to the ascendant trend of Fe (III) adsorbance compared with It is slow before 640mg/g, it is contemplated that adsorbance also increases therewith when continuing to increase concentration in an experiment, therefore chooses solution concentration It is 640mg/g as optium concentration, now maximal absorptive capacity is 631.1300mg/g.Because with Fe (III) concentration Increase, the contact area of SH-LNC/MMT adsorbents and Fe (III) is added, so that the increase of its adsorbance is very fast.
Influence of 2.2 pH value to SH-LNC/MMT adsorbents Fe (III) adsorbance
Influence of the solution ph to SH-LNC/MMT adsorbents Fe (III) adsorbance is as shown in Figure 3.Adsorption experiment condition For:Adsorbent amount is 0.0500g, and 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 before pH=2.0, works as pH value from during 1.71 increase to 2.47 For 1.8 when, SH-LNC/MMT adsorbents are maximum to Fe (III) adsorbance, and now adsorbance is 630.9993mg/g;And in pH After=1.9, SH-LNC/MMT adsorbents are in rising trend to Fe (III) adsorbance, and this is due to the increasing with pH value Greatly, Fe (III) precipitations is more so that the Fe (III) in solution reduces, so that the ferrous iron that can be developed the color with Phen Reduce, so that adsorbance linearly rises.Because Fe (III) begins to precipitate in pH=1.9, in pH=3.2 Precipitation is complete, so it is 1.8 to choose optimal pH.
Influence of 2.3 adsorption temps to SH-LNC/MMT adsorbances
Influence of the adsorption temp to SH-LNC/MMT adsorbents Fe (III) adsorbance is as shown in Figure 4.Adsorption experiment condition For:Adsorbent amount is 0.0500g, and Fe (III) initial concentration solution is 640mg/g, solution ph 1.8, and adsorption time is 40min.As seen from Figure 4, as the rise of adsorption temp, SH-LNC/MMT adsorbents change to Fe (III) adsorbance Irregular, at 40 DEG C, adsorbance is 630.1502mg/g, and adsorbance declines at 45 DEG C, rises again afterwards.In experimentation, Under higher temperature, there is yellow mercury oxide Fe (OH) in the conical flask adsorbed3, it may be possible to because the high temperature within the scope of certain temperature Be advantageous to Fe (OH)3The generation of precipitation, therefore it is 40 DEG C to choose optimal adsorption temperature.
Influence of 2.4 adsorption times to SH-LNC/MMT adsorbances
Influence of the adsorption time to SH-LNC/MMT adsorbents Fe (III) adsorbance is as shown in Figure 5.Adsorption experiment condition For:Adsorbent amount is 0.0500g, and Fe (III) initial concentration solution is 640mg/g, solution ph 1.8, and adsorption temp is 40℃.As seen from Figure 5, with the extension of adsorption time, SH-LNC/MMT adsorbents Fe (III) adsorbance is in 40min When reach maximal absorptive capacity, maximal absorptive capacity 630.4114mg/g.In adsorption process, with the extension of time, adsorbance is in Downward trend after first increasing, because time lengthening is unfavorable for the absorption of adsorbent, therefore do not reach full in the initial stage of absorption, absorption And when, adsorbance increase is more apparent, on a declining curve afterwards.So it is 40min to choose the optimal adsorption time.
3rd, adsorption dynamics adsorption kinetics
Adsorption dynamics adsorption kinetics is to characterize one of most important characteristics of absorption validity, and good dynamics data correlation can be with The absorption mechanism of heavy metal ion in the liquid phase is explained well.Under different Fe (III) initial concentrations, adsorption time is to SH- The influence of LNC/MMT adsorbents Fe (III) adsorbance is as shown in Figure 6.Adsorption experiment condition is:Adsorbent amount is 0.0500g, 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。
The curve of adsorption kinetics of SH-LNC/MMT adsorbents is carried out with pseudo-first-order and quasi- pseudo-second-order kinetic equation Fitting, wherein, pseudo-first-order and quasi- pseudo-second-order kinetic equation are respectively as shown in formula (2) and formula (3):
In formula (2) and formula (3):QeFor adsorption equilibrium when adsorbance (mgg-1);QtFor the suction that adsorption time is t Attached amount (mgg-1);k1The First-order equation speed constant that is defined (min-1);k2The two level that is defined equation speed constant (g (mgmin-1)-1)。
It is 640mg/L in solution concentration, when adsorption temp is 40 DEG C, SH-LNC/MMT adsorbents absorption Fe (III) standard First order dynamic model figure and pseudo-second order kinetic illustraton of model are distinguished as shown in Figure 7 and Figure 8, the adsorption parameters such as institute of table 1 Show.As shown in Table 1:The coefficient R of pseudo-first-order kinetic model2For 0.64417, the coefficient correlation of pseudo-second order kinetic model R2For 0.9999;k2Much smaller than k1;The theoretical adsorbance of pseudo-second order kinetic is 628.9308mg/g, than the theoretical value of pseudo-first-order It is closer to test adsorbance Qe, thus illustrates that SH-LNC/MMT adsorbents meet quasi- two level to Fe (III) absorption behavior Kinetic model, using chemisorbed as primary attachment.
Table 1
4th, adsorption isotherm
Isothermal adsorption rule is under conditions of temperature is constant, investigates the relation between adsorbance and solution equilibria concentration, Its mathematical expression is referred to as adsorption isotherm, and adsorption isotherm is exactly the curve map drawn according to this relation.Fig. 9 is different absorption temperature Under degree (35 DEG C, 40 DEG C, 45 DEG C), influence of Fe (III) initial concentrations to SH-LNC/MMT adsorbents Fe (III) adsorbance.It is real Testing adsorption conditionses is:Adsorbent amount is 0.0500g, solution ph 1.8, adsorption time 40min, adsorption temp difference For:35℃、40℃、45℃.
Langmuir adsorption isotherms can be used by typically adsorbing the adsorption equilibrium relation of solute from liquid or gas to solid Experimental data is analyzed with Freundlich adsorption isotherms.
Shown in Langmuir adsorption isotherms such as formula (4) and formula (5):
Shown in Freundlich adsorption isotherms such as formula (6):
In formula (4), formula (5) and formula (6):QmaxFor the maximum adsorption capacity of Langmuir mono layer adsorptions, mg/g should Parameter shows that more greatly the adsorption capacity of adsorbent is bigger;KLFor the Langmuir constant relevant with absorption energy;CeIt is flat to represent absorption During weighing apparatus in solution adsorbate concentration, mg/L;
QeFor liquid equilibrium when adsorbance, mg/g;KFTo characterize the Freundlich constants of adsorption capacity;N is adsorption strength Index, it is considered that when Freundlich constants 1/n is 0.1-0.5, easily absorption;When 1/n is more than 2, it is difficult to adsorb;pomFor Maximum initial mass concentration, mg/L, works as RLIt is preferential absorption when between 0-1.
It is 520mg/L, 600mg/L, 640mg/L, 680mg/L in solution concentration, adsorption time 40min, adsorption temp Under conditions of 40 DEG C, adsorbent absorption Fe (III) Langmuir and Freundlich Isothermal Models figure such as Figure 10 and Figure 11 It is shown.
SH-LNC/MMT adsorbents are as shown in table 2 to Fe (III) isotherm adsorption model relevant parameter.
Table 2
Model Qmax(mg/L) R2 b kf 1/n
Langmuir 631.1300 0.96049 1.4947
Freundlich 631.1300 0.98907 19.6114 0.6499
From Table 2, it can be seen that in Freundlich isotherm formulas 1/n not in the range of 0.1-0.5, but its be less than 2, institute So that absorption is not highly difficult;The R of Freundlich isotherm formulas2Better than Langmuir, illustrate SH-LNC/MMT adsorbents to Fe (III) adsorption isotherm meets Freundlich isotherm formulas, is multi-molecular absorption.
In summary:SH-LNC/MMT adsorbents are to Fe (III) absorption property by solution ph, initial concentration, absorption Temperature and adsorption time have a great influence.With the increase of solution ph, adsorbent is continuously increased to the adsorbance of Fe (III), Reach optimal adsorption when pH value is 1.8.When solution ph be 1.8, initial concentration 640mg/L, adsorption temp be 40 DEG C and When adsorption time is 40min, SH-LNC/MMT adsorbents are 631.1300mg/g to Fe (III) maximal absorptive capacity, the absorption Agent has good absorption property to Fe (III).SH-LNC/MMT adsorbents meet quasi- second motive force to Fe (III) adsorption process Model and Freundlich isotherm models are learned, illustrates sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent (SH- LNC/MMT) absorption of the adsorbent to Fe (III) based on chemisorbed and is multi-molecular absorption.
Application examples 2
The application example provides sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent that embodiment 1 is prepared The application of Fe (III) ion in waste water is adsorbed, wherein, the application comprises the following steps:
Experimental implementation in the application example is slightly changed with application examples 1, simply experiment condition parameter.
The adsorption experiment condition of the application example is:Adsorbent amount is 0.0500g, and Fe (III) initial concentration solution is 1280mg/g, solution ph 2.1, adsorption temp are 70 DEG C, adsorption time 80min, thus obtained SH-LNC/MMT suctions The attached dose of maximal absorptive capacity to Fe (III) is 596.87mg/g.
Comparative example 1
This comparative example provides lignocellulosic/montmorillonite Composite heavy metal (LNC/MMT) adsorbent in waste water is adsorbed The application of Fe (III) ion, wherein, the application comprises the following steps:
Experimental implementation in this comparative example is slightly changed with application examples 1, simply experiment condition parameter.The absorption of this comparative example Experiment condition is:Adsorbent amount is 0.0500g, and Fe (III) initial concentration solution is 640mg/g, solution ph 1.8, is inhaled Enclosure temperature is 40 DEG C, adsorption time 40min, and thus obtained LNC/MMT adsorbents are to Fe (III) maximal absorptive capacity 271.12mg/g.And the SH-LNC/MMT adsorbents obtained in application examples 1 are 631.13mg/ to Fe (III) maximal absorptive capacity G, adsorption experiment condition are:Adsorbent amount is 0.0500g, and Fe (III) initial concentration solution is 640mg/g, and solution ph is 1.8, adsorption temp is 40 DEG C, adsorption time 40min.It can thus be seen that sulfydryl lignocellulosic/illiteracy provided by the invention Native Compound Heavy Metals adsorbent is taken off to be far above without sulfhydryl modified LNC/ Fe (III) maximal absorptive capacity (631.13mg/g) The maximal absorptive capacity (271.12mg/g) of MMT adsorbents.
Comparative example 2
This comparative example provides lignocellulosic/montmorillonite Composite heavy metal (LNC/MMT) adsorbent in waste water is adsorbed The application of Fe (III) ion, wherein, the application comprises the following steps:
Experimental implementation in this comparative example is slightly changed with application examples 1, simply experiment condition parameter.The absorption of this comparative example Experiment condition is:Adsorbent amount is 0.0500g, and Fe (III) initial concentration solution is 1280mg/g, solution ph 2.1, is inhaled Enclosure temperature is 70 DEG C, adsorption time 80min, and thus obtained LNC/MMT adsorbents are to Fe (III) maximal absorptive capacity 452.06mg/g.And the SH-LNC/MMT adsorbents obtained in application examples 2 are 596.87mg/ to Fe (III) maximal absorptive capacity G, adsorption experiment condition are:Adsorbent amount is 0.0500g, and Fe (III) initial concentration solution is 1280mg/g, and solution ph is 2.1, adsorption temp is 70 DEG C, adsorption time 80min.It can thus be seen that sulfydryl lignocellulosic/illiteracy provided by the invention Native Compound Heavy Metals adsorbent is taken off to be higher than without sulfhydryl modified LNC/ Fe (III) maximal absorptive capacity (596.87mg/g) The maximal absorptive capacity (452.06mg/g) of MMT adsorbents.
Application examples 3
The application example provides sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent that embodiment 1 is prepared The application of Cu (II) ion in waste water is adsorbed, wherein, the application comprises the following steps:
1st, standard working curve is drawn
1.0mL, 1.2mL, 1.4mL, 1.6mL, 2.0mL Cu (II) standard liquid are accurately added in 50mL volumetric flasks (concentration 10ug/mL), 2mL citric acid solution, 4mL ammonia spirit, 10mL bisoxalydihydrazone (BCO) are molten Liquid, shake up, be diluted to scale.(instrument preheats 10min) is blank with distilled water with 610nm wavelength, 3cm cuvettes after 10min Reference, absorbance is measured, then using concentration as abscissa, absorbance is that ordinate draws standard working curve, obtains its standard song Line equation, as shown in figure 12.
2nd, Cu (II) ion in sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent absorption waste water
The accurate SH-LNC/MMT adsorbents for weighing 0.0500g, are added in Cu (II) solution of 50mL concentration knowns, put In water-bath constant temperature oscillator (120rpm), after reaching adsorption equilibrium under certain condition, centrifuge (rotating speed 6000rpm), Supernatant liquid 5mL is taken, then using determined by ultraviolet spectrophotometry absorbance, calculates the residual concentration of Cu (II) in solution.
Adsorption experiment is carried out under different Cu (II) initial concentration, pH value, adsorption temp and adsorption time, by formula (7) Calculate adsorbance of the SH-LNC/MMT adsorbents to Cu (II).
In formula (7), Q is adsorbance (mg/g);C0And CtRespectively Cu (II) initial concentration and remaining for t Cu (II) Remaining concentration (mol/L);The volume (L) of Cu (II) solution when V is absorption;M is adsorbent mass (g).
Influence of 2.1 solution concentrations to SH-LNC/MMT adsorbents Cu (II) adsorbance
Influence of Cu (II) initial concentration to SH-LNC/MMT adsorbents Cu (II) adsorbance is as shown in figure 13.Absorption is real The condition of testing is:Adsorbent amount is 0.0500g, and pH value 4.0, adsorption temp is 20 DEG C, adsorption time 60min.By Figure 13 As can be seen that with the increase of Cu (II) initial concentration solution, SH-LNC/MMT adsorbents increase the adsorbance of copper ion.When When Cu (II) concentration is 0.04mol/L, tend to balance substantially, adsorbance 342.56mg/g.Then, with copper ion concentration Continue increase, adsorbance tends towards stability and fluctuated in smaller range.It is thus determined that optimal adsorption concentration is 0.04mol/L.
Influence of 2.2 pH value to SH-LNC/MMT adsorbents Cu (II) adsorbance
Influence of the solution ph to SH-LNC/MMT adsorbents Cu (II) adsorbance is as shown in figure 14.Adsorption experiment condition For:Adsorbent amount is 0.0500g, and Cu (II) initial concentration solution is 0.04mol/L, and adsorption temp is 20 DEG C, adsorption time For 60min.As seen from Figure 14, when pH value is more than 3.0, with the increase of liquid phase PH valve, suction of the adsorbent to copper ion Attached amount is slowly increased in a certain scope (pH value 3.0-4.0).Its main cause is adsorption saturation, also have partly cause be because For montmorillonite surface it is dissociable go out compared with polyhydroxy, make adsorbent surface positive charge intensive, same sex electric charge is mutually exclusive to have impact on suction Attached dose of further absorption;But when continuing to increase acidity, adsorbance can rise, and this is primarily due to larger in pH value Under environment, the precipitation for Cu (II) occur is had begun to.It is possible thereby to determine, the optimal pH scope of adsorption process is 4.0 or so.
Influence of 2.3 adsorption temps to SH-LNC/MMT adsorbances
Influence of the adsorption temp to SH-LNC/MMT adsorbents Cu (II) adsorbance is as shown in figure 15.Adsorption experiment condition For:Adsorbent amount is 0.0500g, and Cu (II) initial concentration solution is 0.04mol/L, solution ph 4.0, and adsorption time is 60min.As seen from Figure 15, temperature is from during 10 DEG C are raised to 80 DEG C, SH-LNC/MMT adsorbents absorption copper ion Ability shows the process for first raising and being gradually reduced afterwards, illustrates that adsorbent is one to the adsorption process of copper ion and increased with temperature Add, the exothermic process that the system degree of disorder reduces, it can be seen that absorption of the adsorbent to copper ion is based on chemisorbed.Therefore select It is 20 DEG C to take optimum temperature.
Influence of 2.4 adsorption times to SH-LNC/MMT adsorbances
Influence of the adsorption time to SH-LNC/MMT adsorbents Cu (II) adsorbance is as shown in figure 16.Adsorption experiment condition For:Adsorbent amount is 0.0500g, and Cu (II) initial concentration solution is 0.04mol/L, solution ph 4.0, and adsorption temp is 20℃.As seen from Figure 16, when reacted between when within 60min, adsorbent is to Cu (II) adsorbance with adsorption time Extension it is on the rise, when adsorption time reaches 60min, adsorbance reaches maximum, keeps homeostasis substantially afterwards, whole to inhale The trend that attached process adsorbance tends to balance afterwards with time lengthening in first increasing.Therefore the selection optimal adsorption time is 60min.
3rd, adsorption dynamics adsorption kinetics
When carrying out data processing to adsorption dynamics adsorption kinetics, the optimum condition of selection is:Concentration is 0.04mol/L, absorption temperature Spend for 20 DEG C, solution ph 4.0.Curve of adsorption kinetics pseudo-first-order and quasi- secondary absorption to SH-LNC/MMT adsorbents Kinetics equation carries out linear regression fit:Wherein, pseudo-first-order and quasi- pseudo-second-order kinetic equation are respectively such as formula (8), formula (9) It is shown:
In formula (8), formula (9):qeFor adsorption equilibrium when adsorbance (mgg-1);qtFor the suction that adsorption time is t Attached amount (mgg-1);k1The First-order equation speed constant that is defined (min-1);k2The two level that is defined equation speed constant (g (mgmin-1)-1)。
It is 0.04mol/L in solution concentration, adsorption temp is 20 DEG C, when solution ph is 4.0, SH-LNC/MMT adsorbents The one-level of Adsorption of Cu (II), second-order kinetics illustraton of model are respectively as shown in Figure 17, Figure 18.From Figure 17, Figure 18, SH-LNC/ The adsorption dynamics adsorption kinetics of MMT adsorbents does not meet pseudo-first-order kinetic model, but meets pseudo-second order kinetic model, coefficient R2 =0.9929.Therefore, absorption of the SH-LNC/MMT to Cu (II) meets quasi- secondary absorption rate equation, based on chemisorbed.
4th, adsorption isotherm
Isothermal adsorption rule is under conditions of temperature is constant, investigates the relation between adsorbance and solution equilibria concentration, Its mathematical expression is referred to as adsorption isotherm, and adsorption isotherm is exactly the curve map drawn according to this relation.Typically to solid from liquid The adsorption equilibrium pass of solute is adsorbed in body or gas can use Langmuir adsorption isotherms and Freundlich adsorption isotherms pair Experimental data is analyzed.Calculated using such as following formula (10) and formula (11):
In formula (10) and formula (11):B is the Langmuir constant (Lmg relevant with absorption energy-1);n、KfFor Freundlich constants;CeFor adsorption equilibrium when solution in remaining Cu (II) concentration, (molL-1);qmaxSatisfy for monolayer With adsorbance (mgg-1);qeFor Cu (II) equilibrium adsorption capacity (mgg-1)。
Langmuir the and Freundlich Isothermal Models figure of adsorbent Adsorption of Cu (II) is as illustrated in figures 19 and 20.
From Figure 19 and Figure 20 fitting result, absorption of the SH-LNC/MMT adsorbents to Cu (II) more meets Langmuir isotherm adsorption models.Linearly dependent coefficient R2=0.9465, illustrate that the adsorption process belongs to mono layer adsorption.
In summary:Using SH-LNC/MMT adsorbents, in Cu (II) adsorption process, the adsorbent is to concentration 0.04mol/L Cu (II) adsorption effect is optimal, and its optimal adsorption temperature is 20 DEG C, and close to room temperature, this is to industrial wastewater Absorption for be the condition being easily met, cost absorption can be reduced.Optimal adsorption time of the adsorbent to Cu (II) For one hour or so, extend adsorption time, adsorbance has downward trend on the contrary in certain section.And acidity is to the shadow of the process Sound is mainly manifested in, and sulfydryl can not realize good absorption because of inactivation when acidity is smaller;When acidity is larger, copper ion is again Precipitation, which can be started, causes the measure of adsorbance to be affected.Therefore, optimal adsorption condition is that Cu (II) initial concentration is 0.04mol/L, pH value 4.0, adsorption temp are 20 DEG C, adsorption time 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 models.
Application examples 4
The application example provides sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent that embodiment 1 is prepared The application of Cu (II) ion in waste water is adsorbed, wherein, the application comprises the following steps:
Experimental implementation in the application example is slightly changed with application examples 3, simply experiment parameter.The adsorption experiment of the application example Condition is:SH-LNC/MMT adsorbent amounts are 0.0500g, and Cu (II) initial concentration solution is 0.03mol/L, and solution ph is 4.9, adsorption temp is 50 DEG C, and adsorption time 60min, SH-LNC/MMT adsorbent is to Cu (II) maximal absorptive capacity 338.16mg/g。
Comparative example 3
This comparative example provides lignocellulosic/montmorillonite Composite heavy metal (LNC/MMT) adsorbent in waste water is adsorbed The application of Cu (II) ion, wherein, the application comprises the following steps:
Experimental implementation in this comparative example is slightly changed with application examples 3, simply experiment parameter.The adsorption experiment of this comparative example Condition is:Adsorbent amount is 0.0500g, and Cu (II) initial concentration solution is 0.04mol/L, solution ph 4.0, adsorbs temperature Spend for 20 DEG C, adsorption time 60min, thus obtained LNC/MMT adsorbents are to Cu (II) maximal absorptive capacity 196.25mg/g.And the SH-LNC/MMT adsorbents obtained in application examples 3 are 342.56mg/g to Cu (II) maximal absorptive capacity, Adsorption experiment condition is:Adsorbent amount is 0.0500g, and Cu (II) initial concentration is 0.04mol/L, pH value 4.0, is adsorbed Temperature is 20 DEG C, adsorption time 60min.It can thus be seen that sulfydryl lignocellulosic/montmorillonite provided by the invention is multiple Heavy metal absorbent is closed to be higher than without sulfhydryl modified LNC/MMT adsorbents Cu (II) maximal absorptive capacity (342.56mg/g) Maximal absorptive capacity (196.25mg/g).
Comparative example 4
This comparative example provides lignocellulosic/montmorillonite Composite heavy metal (LNC/MMT) adsorbent in waste water is adsorbed The application of Cu (II) ion, wherein, the application comprises the following steps:
Experimental implementation in this comparative example is slightly changed with application examples 3, simply experiment parameter.The adsorption experiment of this comparative example Condition is:Adsorbent amount is 0.0500g, and Cu (II) initial concentration solution is 0.03mol/L, solution ph 4.9, adsorbs temperature Spend for 50 DEG C, adsorption time 60min, thus obtained LNC/MMT adsorbents are to Cu (II) maximal absorptive capacity 322.56mg/g.And the SH-LNC/MMT adsorbents obtained in application examples 4 are 338.16mg/g to Cu (II) maximal absorptive capacity, Adsorption experiment condition is:SH-LNC/MMT adsorbent amounts are 0.0500g, and Cu (II) initial concentration solution is 0.03mol/L, molten Liquid pH value is 4.9, and adsorption temp is 50 DEG C, adsorption time 60min.It can thus be seen that sulfydryl provided by the invention is wooden Cellulose/montmorillonite Composite heavy metal absorbent is higher than without sulfhydryl modified to Cu (II) maximal absorptive capacity (338.16mg/g) LNC/MMT adsorbents maximal absorptive capacity (322.56mg/g).

Claims (12)

1. a kind of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent, wherein, the adsorbent is by sulfydryl wood fibre What element formed with montmorillonite Composite;
The sulfydryl lignocellulosic and the mass ratio of montmorillonite are 1:1-1.5:1;The sulfydryl lignocellulosic intercalation enters Between the lamella of the montmorillonite;
The preparation method of the sulfydryl lignocellulosic comprises the following steps:
TGA and acetic anhydride are well mixed, after cooling, lignocellulosic is added, is reacted under water-bath, then by reaction product Dried after washing to neutrality, obtain the sulfydryl lignocellulosic;
The TGA, acetic anhydride, the mass ratio of lignocellulosic are 5-6:2-3:1;
The preparation method of the sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent comprises the following steps:
A, sulfydryl lignocellulosic is added in sodium hydrate aqueous solution, obtains the suspension of sulfydryl lignocellulosic;
B, montmorillonite is added to the water, obtains the suspension of montmorillonite;
C, the suspension of the montmorillonite is added in the suspension of sulfydryl lignocellulosic, heating makes its reaction, and reaction is produced Thing is washed to neutrality, after drying, obtains the sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent;
The heavy metal is iron.
2. sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent according to claim 1, wherein, the sulfydryl The granularity of lignocellulosic/montmorillonite Composite heavy metal absorbent is 150-200 mesh.
3. sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent according to claim 1, wherein, the cooling To be cooled to room temperature.
4. sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent according to claim 1, wherein, the water-bath Temperature be 40-45 DEG C, reaction time 45-48h.
5. sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent according to claim 1, wherein, the drying Temperature be 40-50 DEG C.
6. the preparation method of sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent described in claim any one of 1-5, Wherein, this method comprises the following steps:
A, sulfydryl lignocellulosic is added in sodium hydrate aqueous solution, obtains the suspension of sulfydryl lignocellulosic;B, will cover De- soil is added to the water, and obtains the suspension of montmorillonite;
C, the suspension of the montmorillonite is added in the suspension of sulfydryl lignocellulosic, heating makes its reaction, and reaction is produced Thing is washed to neutrality, after drying, obtains the sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent.
7. preparation method according to claim 6, wherein, the quality and hydrogen-oxygen of sulfydryl lignocellulosic described in step a The ratio for changing the volume of sodium water solution is 1:30-1:35, unit is respectively g and mL.
8. preparation method according to claim 6, wherein, the concentration of the sodium hydrate aqueous solution is 0.1-0.2mol/ L。
9. preparation method according to claim 6, wherein, sulfydryl lignocellulosic described in step b and the matter of montmorillonite Amount is than being 1:1-1.5:1;The ratio of the quality of montmorillonite and the volume of water described in step b is 1:30-1:40, unit is respectively G and mL.
10. preparation method according to claim 6, wherein, the temperature of heating response described in step c is 60-65 DEG C, instead It is 6-8h between seasonable.
11. preparation method according to claim 6, wherein, drying is 100-110 DEG C of dry 8-10h described in step c.
12. sulfydryl lignocellulosic/montmorillonite Composite heavy metal absorbent described in claim any one of 1-5 is in removing waste water Application in institute's iron content.
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