CN108585101B - Recovery method of inorganic material hybridized porous biomass microspheres for heavy metal sewage treatment - Google Patents
Recovery method of inorganic material hybridized porous biomass microspheres for heavy metal sewage treatment Download PDFInfo
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Abstract
The invention belongs to the technical field of biomass, and particularly relates to an inorganic material hybridized porous biomass microsphere for heavy metal sewage treatment and a preparation method thereof. The invention takes modified sorghum stalks and modified hectorite as raw materials to be compounded into inorganic material hybridized porous biomass microspheres; the prepared composite material can adsorb heavy metal ions, aniline and phenol organic pollutants in wastewater, and the phenol adsorption removal rate is up to 99%.
Description
Original application No. 2017110184467, entitled porous biomass microsphere for heavy metal sewage treatment and preparation method thereof, filing date 2017.10.27.
Technical Field
The invention belongs to the technical field of biomass, and particularly relates to a recovery method of inorganic material hybridized porous biomass microspheres for heavy metal sewage treatment.
Background
With the continuous development of the industrial development process, the soil in China is seriously polluted, wherein the heavy metal pollution causes the main types of soil pollution, and the main types of pollutants are chromium (Cd), nickel (Ni), copper (Cu), mercury (Hg), lead (Pb) and the like. At present, the overproof point of heavy metal in farmland soil in China is mainly polluted by low-medium heavy metal, so that in order to achieve the dual purposes of normal agricultural production and soil heavy metal restoration, a modifier (commonly called a passivator) is usually added into soil to convert the heavy metal into a low-dissolved, fixed and low-toxicity form, so that the enrichment of the heavy metal in a plant body is reduced, and the purpose of reducing the environmental risk of polluting the heavy metal while ensuring the agricultural production is achieved.
At present, widely used soil passivation restoration agents mainly comprise two categories of inorganic passivators and organic passivators; wherein phosphate compounds such as Hydroxyapatite (HAP) are passivation repair agents widely used at present. Cell field experiments verify that micron-sized HAP can effectively reduce the content of exchangeable-state and carbonate-bound-state Cu in soil and reduce the ecological environment risk of Cu in Hutian fields (Hutian fields, research on repairing heavy metal copper and lead polluted soil by nano hydroxyapatite [ D ]. Anhui agriculture university, 2012).
The southern China agricultural university discloses a biomass charcoal soil heavy metal restoration agent (CN 105622290A), which is characterized in that the biomass charcoal obtained by calcining chicken manure or oil tea shells at the high temperature of 550 ℃ through 450-; CN 102583619A reports a method for adsorbing heavy metals by composite biomass, which takes Chinese chestnut peel, rice aboveground biomass and typha overground biomass as raw materials to form composite biomass, and can remove various heavy metals in an aqueous solution by adsorption. Mawei et al (CN 103316640B) at university of continental engineering developed a magnetic biomass adsorbent for removing heavy metals, which was prepared by pulverizing and mixing wood flour, fruit shell, and corn stalk biomass as raw materials, mixing the pulverized and mixed materials with a chitosan solution of acetic acid, adding a magnetic substance, and solidifying the mixture with an alkali solution to obtain a magnetic biomass adsorbent.
Disclosure of Invention
The invention aims to provide a novel inorganic hybrid biomass material, which is prepared by compounding modified sorghum stalks and modified hectorite serving as raw materials; the prepared composite material can adsorb heavy metal ions, aniline and phenol organic pollutants in wastewater, and the phenol adsorption removal rate is up to 99%.
According to one aspect of the invention, the invention provides inorganic material hybridized porous biomass microspheres, which are hybridized by sorghum stalks and hectorite;
the preparation method of the inorganic material hybridized porous biomass microspheres comprises the following steps:
1) modification of sorghum stalks:
a) a crushing procedure: drying sorghum stalks in the air, and crushing the sorghum stalks to obtain sorghum stalk biomass particles with the particle size of below 200 meshes;
b) acid and alkali treatment: placing 100g of sorghum stalk biomass particles into 3wt% phosphoric acid aqueous solution, stirring and soaking for 30min, then placing into 5wt% potassium hydroxide aqueous solution, soaking for 10min at 50 ℃, filtering, washing with tap water until the filtrate is neutral to obtain acid-base modified biomass particles; the phosphoric acid aqueous solution and the potassium hydroxide aqueous solution are preferably used for immersing the sorghum stalk biomass particles;
c) an oxidation process: placing the acid-base modified biomass particles in a potassium permanganate aqueous solution with the concentration of 5wt% for oxidation treatment for 1-2h to obtain an oxidized biomass dispersion liquid; the biomass contains a large amount of cellulose and hemicellulose, and potassium permanganate is adopted to oxidize to form naked carboxyl;
d) grafting reaction: then adding N- (tert-butyloxycarbonyl) aminoacetic acid and concentrated sulfuric acid to react for 2h at 40 ℃, and then reacting for 2h at 70 ℃; filtering, washing with water until the filtrate becomes neutral, and drying to obtain glycine grafted biomass; forming acid anhydride by the amino acetic acid and the exposed carboxyl formed in the oxidation procedure under the action of concentrated sulfuric acid, and removing the protecting group to expose amino and salifying with sulfuric acid;
2) preparing composite modified hectorite:
(1) quaternization of hectorite: placing hectorite with the particle size of less than 200 meshes in an aqueous solution of octadecyl dimethyl benzyl ammonium chloride, and performing ultrasonic dispersion for 48 hours to obtain a quaternary ammonium salinized hectorite dispersion liquid; 0.12-0.20g octadecyl dimethyl benzyl ammonium chloride is needed for each gram of hectorite;
(2) complexation of hectorite: adding ethylenediamine into the hectorite dispersion liquid for complexing, stirring at 40 ℃ for 12h, and then filtering until the filtrate is free of chloride ions detected by silver nitrate; drying at 70 ℃ to obtain the composite modified hectorite; 0.05-0.10g of ethylenediamine per gram of hectorite; in the step, ethylenediamine is loaded on the quaternized hectorite through complexation;
3) preparing inorganic material hybridized porous biomass microspheres:
placing 10g of composite modified hectorite and 8g of glycine grafted biomass in 100ml of ethanol water solution, uniformly stirring, adding 0.1g of triethylamine, adding a cross-linking agent glutaraldehyde, carrying out reflux reaction for 2h, filtering, washing with water, and drying to obtain the inorganic material hybridized porous biomass microspheres. The triethylamine is added in the invention to dissociate sulfate of amino in the glycine grafted biomass, so that amino on the biomass, hectorite loaded amino sites and glutaraldehyde are crosslinked to form a composite material;
preferably, the oxidation treatment temperature in the oxidation procedure is 10-20 ℃, and the using amount of potassium permanganate is 0.08-0.13 time of the weight of the sorghum stalk biomass particles; the sorghum stalks contain a large amount of cellulose and hemicellulose, and the carbon-carbon bonds of the cellulose and the hemicellulose in the biomass are oxidized and broken in the oxidation process to form partial carboxyl; potassium permanganate is generally low in selectivity, and the oxidation temperature directly determines the degree of subsequent grafting reaction, so that the morphology and the physicochemical property of the final inorganic material hybridized porous biomass microspheres are influenced;
preferably, the dosage of the N- (tert-butyloxycarbonyl) glycine in the grafting reaction is 0.21-0.32 time of the weight of the sorghum stalk biomass particles;
preferably, the dosage of the cross-linking agent glutaraldehyde is 0.3-0.5 g;
preferably, the drying temperature in the preparation process of the inorganic material hybridized porous biomass microspheres is 65 ℃, and the specific surface area reaches 79.2m2.g-1(ii) a In research, the drying temperature influences the specific surface area of the porous biomass microspheres in the preparation process of the inorganic material hybridized porous biomass microspheres, the specific surface area is smaller when the porous biomass microspheres are naturally dried at 20-30 ℃, and the pore diameter of the microspheres is enlarged due to the gradual collapse of the biomass structure in the porous biomass microspheres above 70 ℃, so that the adsorption of heavy metals or organic pollutants is not facilitated.
According to another aspect of the invention, the invention provides a use of inorganic material hybridized porous biomass microspheres for adsorbing heavy metal ions, phenol and aniline in wastewater under a certain pH value environment; the heavy metal is Pb2+、Cr2+、Cu2+、Ni2+Or Zn2+(ii) a The inorganic material hybridized porous biomass microsphere prepared by the invention has nitrogen-oxygen electron-rich groups, can provide adsorption binding sites with heavy metal ions, and can adsorb organic pollutants through hydrogen bonds and a porous structure.
According to the application of the inorganic material hybridized porous biomass microspheres, the inorganic material hybridized porous biomass microspheres are used for adsorbing heavy metal ions, phenol and aniline in wastewater under the environment with a certain pH value; the heavy metal is Pb2+、Cr2+、Cu2+、Ni2+Or Zn2+(ii) a Under the environment with different pH values, the inorganic material hybridized porous biomass microspheres have different adsorption effects on heavy metals, aniline and phenols, and adsorb Pb2+、Cr2+、Cu2+、Ni2+Or Zn2+The pH environment of (A) is as follows: pb2+4.3-5.2 of Cr2+5.2 to 5.5, Cu2+Is 6.2 to 6.5, Ni2+4.3-4.8; zn2+3.2 to 7.8; the pH environment for adsorbing phenol is 5.5-6.4, and the pH environment for adsorbing aniline is 7.8-8.2.
After the inorganic material hybridized porous biomass microspheres prepared by the invention are used for adsorbing heavy metals, the heavy metals adsorbed by the inorganic material hybridized porous biomass microspheres can be desorbed by a hydrochloric acid solution, and the desorbed inorganic material hybridized porous biomass microspheres can be recycled after being activated by heat treatment.
Compared with the prior art, the invention has the following advantages:
1) the invention provides a novel inorganic material hybridized porous biomass microsphere prepared by compounding modified sorghum stalks and modified hectorite serving as raw materials, which has excellent specific surface area reaching 79.2m2.g-1；
2) The porous biomass microspheres prepared by the invention can be used for adsorbing various heavy metal ions and can adsorb aniline and/or phenol at the same time;
3) heavy metal adsorbed by the porous biomass microspheres prepared by the method can be desorbed by hydrochloric acid solution, and the porous biomass microspheres subjected to heat treatment after acid desorption can be reused for adsorbing heavy metal again.
Drawings
FIG. 1 is an electron microscope scanning image of inorganic material hybridized porous biomass microsphere prepared by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention.
Example 1
Preparing inorganic material hybridized porous biomass microspheres:
1) modification of sorghum stalks:
a) a crushing procedure: drying sorghum stalks in the air, and crushing the sorghum stalks to obtain sorghum stalk biomass particles with the particle size of below 200 meshes;
b) acid and alkali treatment: placing 100g of sorghum stalk biomass particles into 200ml of 3wt% phosphoric acid aqueous solution, stirring and soaking for 30min, then placing into 200ml of 5wt% potassium hydroxide aqueous solution, soaking for 10min at 50 ℃, filtering, washing with tap water until the filtrate is neutral to obtain acid-base modified biomass particles;
c) an oxidation process: placing the acid-base modified biomass particles in a 5wt% potassium permanganate aqueous solution, and carrying out oxidation treatment at 10-20 ℃ for 1-2h to obtain an oxidized biomass dispersion liquid; the using amount of the potassium permanganate is 0.10 time of the weight of the sorghum stalk biomass particles;
d) grafting reaction: then adding N- (tert-butyloxycarbonyl) aminoacetic acid and concentrated sulfuric acid to react for 2h at 40 ℃, and then reacting for 2h at 70 ℃; filtering, washing with water until the filtrate becomes neutral, and drying to obtain glycine grafted biomass; the dosage of the N- (tert-butyloxycarbonyl) glycine in the grafting reaction is 0.26 time of the weight of the sorghum stalk biomass particles;
2) preparing composite modified hectorite:
(1) quaternization of hectorite: placing 100g of hectorite with the particle size of below 200 meshes in an aqueous solution of octadecyl dimethyl benzyl ammonium chloride (0.12-0.20 g of octadecyl dimethyl benzyl ammonium chloride is needed per gram of hectorite), wherein the dosage of the example is that (0.15 g of octadecyl dimethyl benzyl ammonium chloride is needed per gram of hectorite), and performing ultrasonic dispersion for 48 hours to obtain a quaternary ammonified hectorite dispersion liquid;
(2) complexation of hectorite: adding ethylenediamine (taking the hectorite in the step 1 as a calculation base number, 0.05-0.10g of ethylenediamine is needed for each gram of hectorite, and the dosage of the embodiment is 0.08g of ethylenediamine is needed for each gram of hectorite) into the hectorite dispersion liquid for complexing, stirring for 12h at 40 ℃, filtering until no chloride ion is detected by silver nitrate in filtrate, and drying at 70 ℃ to obtain the composite modified hectorite;
3) preparing inorganic material hybridized porous biomass microspheres:
placing 10g of composite modified hectorite and 8g of glycine grafted biomass in 100ml of ethanol aqueous solution, uniformly stirring, adding 0.1g of triethylamine, then adding a cross-linking agent glutaraldehyde (0.4 g), carrying out reflux reaction for 2 hours, filtering, washing with water, and drying at 65 ℃ to constant weight to obtain the inorganic material hybridized porous biomass microspheres.
Example 2 Effect of different drying temperatures on the specific surface area of porous Biomass microspheres
(a) Compared with the embodiment 1, the difference lies in that the drying temperature in the preparation process of the inorganic material hybridized porous biomass microspheres is 20-30 ℃, and the rest preparation process and the raw material proportion are completely the same as the embodiment 1;
(b) compared with the example 1, the difference lies in that the drying temperature in the preparation process of the inorganic material hybridized porous biomass microspheres is 80-90 ℃, and the rest preparation process and the raw material proportion are completely the same as the example 1.
Example 3
Inorganic material hybridized porous biomass microspheres are adopted to adsorb heavy metals in aqueous solution, and the specific method is as follows, Pb is prepared respectively2+、Cr2+、Cu2+、Ni2+Or Zn2+The molar concentration of the chloride aqueous solution is 60 mmol/L; in addition, preparing aqueous solutions of aniline and phenol respectively, wherein the molar concentration is also 60 mmol/L; taking the inorganic material hybridized porous biomass microspheres prepared in the example 1 as an adsorbent (1.0 g of the adsorbent is added into each liter of aqueous solution), placing the inorganic material hybridized porous biomass microspheres in an aqueous solution of heavy metal or organic matter (aniline or phenol) at the room temperature of 20-30 ℃, adjusting the pH of the system to a certain interval by using hydrochloric acid or sodium hydroxide, stirring and adsorbing for 2 hours, filtering, testing the concentrations of aniline and phenol in filtrate by using an ultraviolet detector, measuring the concentration of heavy metal ions in the filtrate by using atomic absorption, and calculating the absorption efficiency; the results are shown in table 1 below:
TABLE 1 adsorption capacity of porous biomass microspheres for adsorbing heavy metals and organic pollutants
Note: 1) the removal efficiency is the average value of three points in the pH value interval, namely two end points and a middle value of the pH value interval; examples 2.0 to 3.0, i.e., pH of 2.0. + -. 0.1, 2.5. + -. 0.1, and 3.0. + -. 0.1, respectively, which correspond to the average values of the adsorption efficiencies, 2) phenol + Cr2+The system represents phenol and CrCl2The concentration of the mixed solution is 60mmol/L, the dosage of the adsorbent is the same as that 1.0g of adsorbent is added into each liter of the aqueous solution, the adsorption temperature is also 20-30 ℃, and the adsorption time is 2 h.
The porous biomass microspheres prepared according to the preparation methods in (a) and (b) of example 2 were subjected to adsorption test (test conditions are the same as above, i.e., temperature, adsorbent amount, initial concentration, etc.), and the results are shown in table 2:
TABLE 2 Effect of different drying temperatures on the adsorption Properties of the adsorbents
Because heavy metals can be desorbed with the adsorbent under acidic conditions, the invention tries to desorb the heavy metals after the adsorbent is used according to the principle, and the specific method is as follows: filtering and recovering inorganic material hybridized porous biomass microspheres, placing the microspheres in 2mol/L hydrochloric acid aqueous solution for ultrasonic treatment at 50 ℃ for 2h, and measuring Pb2+、Cr2+、Cu2+、Ni2+Or Zn2+The desorption rate of heavy metal ions, the desorbed adsorbent is dried in vacuum at 50 ℃ to constant weight, and the adsorbent with desorption rate greater than 90% is reused to test the adsorption rate after recovery (the test method is the same as above), and the results are shown in table 3:
TABLE 3 desorption rate of the adsorbent under acidic condition and its adsorption performance after recovery and reuse
Note: "-" indicates that the adsorption rate test was not performed due to too low desorption rate, wherein Cu was present2+The adsorption pH environment is 7.0 when the recovery sleeve is used; ni2+The adsorption pH environment is 4.5 when the recovery sleeve is used.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (2)
1. Cu2+The method for recovering the inorganic material hybridized porous biomass microspheres for heavy metal sewage treatment is characterized by comprising the following steps of: filtering and recovering inorganic material hybridized porous biomass microspheres, putting the microspheres into 2mol/L hydrochloric acid aqueous solution, performing ultrasonic treatment at 50 ℃ for 2h, and measuring Cu2+The desorption rate of heavy metal ions, and the desorbed adsorbent is dried in vacuum at 50 ℃ to constant weight to obtain the recovered inorganic material hybridized porous biomass microspheres;
the recycled inorganic material hybridized porous biomass microspheres are used for adsorbing Cu in the environment with the pH of 7.02+Waste water;
the inorganic material hybridized porous biomass microsphere is prepared by the following preparation method:
1) modification of sorghum stalks:
a) a crushing procedure: drying sorghum stalks in the air, and crushing the sorghum stalks to obtain sorghum stalk biomass particles with the particle size of below 200 meshes;
b) acid and alkali treatment: placing 100g of sorghum stalk biomass particles into 200ml of 3wt% phosphoric acid aqueous solution, stirring and soaking for 30min, then placing into 200ml of 5wt% potassium hydroxide aqueous solution, soaking for 10min at 50 ℃, filtering, washing with tap water until the filtrate is neutral to obtain acid-base modified biomass particles;
c) an oxidation process: placing the acid-base modified biomass particles in a 5wt% potassium permanganate aqueous solution, and carrying out oxidation treatment at 10-20 ℃ for 1-2h to obtain an oxidized biomass dispersion liquid; the using amount of the potassium permanganate is 0.10 time of the weight of the sorghum stalk biomass particles;
d) grafting reaction: then adding N- (tert-butyloxycarbonyl) aminoacetic acid and concentrated sulfuric acid to react for 2h at 40 ℃, and then reacting for 2h at 70 ℃; filtering, washing with water until the filtrate becomes neutral, and drying to obtain glycine grafted biomass; the dosage of the N- (tert-butyloxycarbonyl) glycine in the grafting reaction is 0.26 time of the weight of the sorghum stalk biomass particles;
2) preparing composite modified hectorite:
(1) quaternization of hectorite: placing 100g of hectorite with the granularity of less than 200 meshes in an aqueous solution of octadecyl dimethyl benzyl ammonium chloride, and performing ultrasonic dispersion for 48 hours to obtain a quaternary ammonium salinized hectorite dispersion liquid; 0.15g octadecyl dimethyl benzyl ammonium chloride per gram hectorite is required;
(2) complexation of hectorite: adding ethylenediamine into the hectorite dispersion liquid, wherein each gram of hectorite needs 0.08g of ethylenediamine for complexing, stirring for 12 hours at 40 ℃, then filtering until filtrate is free of chloride ions detected by silver nitrate, and drying at 70 ℃ to obtain composite modified hectorite;
(3) preparing inorganic material hybridized porous biomass microspheres:
placing 10g of composite modified hectorite and 8g of glycine grafted biomass into 100ml of ethanol water solution, uniformly stirring, adding 0.1g of triethylamine, then adding 0.4g of cross-linking agent glutaraldehyde, carrying out reflux reaction for 2 hours, filtering, washing with water, and drying at 65 ℃ to constant weight to obtain the inorganic material hybridized porous biomass microspheres.
2. Ni2+The method for recovering the inorganic material hybridized porous biomass microspheres for heavy metal sewage treatment is characterized by comprising the following steps of: filtering and recovering inorganic material hybridized porous biomass microspheres, putting the microspheres into 2mol/L hydrochloric acid aqueous solution, performing ultrasonic treatment at 50 ℃ for 2h, and measuring Ni2+The desorption rate of heavy metal ions, and the desorbed adsorbent is dried in vacuum at 50 ℃ to constant weight to obtain the recovered inorganic material hybridized porous biomass microspheres;
the recycled inorganic material hybridized porous biomass microspheres are used for adsorbing Ni in the environment with pH of 4.52+Waste water;
the inorganic material hybridized porous biomass microsphere is prepared by the following preparation method:
1) modification of sorghum stalks:
a) a crushing procedure: drying sorghum stalks in the air, and crushing the sorghum stalks to obtain sorghum stalk biomass particles with the particle size of below 200 meshes;
b) acid and alkali treatment: placing 100g of sorghum stalk biomass particles into 200ml of 3wt% phosphoric acid aqueous solution, stirring and soaking for 30min, then placing into 200ml of 5wt% potassium hydroxide aqueous solution, soaking for 10min at 50 ℃, filtering, washing with tap water until the filtrate is neutral to obtain acid-base modified biomass particles;
c) an oxidation process: placing the acid-base modified biomass particles in a 5wt% potassium permanganate aqueous solution, and carrying out oxidation treatment at 10-20 ℃ for 1-2h to obtain an oxidized biomass dispersion liquid; the using amount of the potassium permanganate is 0.10 time of the weight of the sorghum stalk biomass particles;
d) grafting reaction: then adding N- (tert-butyloxycarbonyl) aminoacetic acid and concentrated sulfuric acid to react for 2h at 40 ℃, and then reacting for 2h at 70 ℃; filtering, washing with water until the filtrate becomes neutral, and drying to obtain glycine grafted biomass; the dosage of the N- (tert-butyloxycarbonyl) glycine in the grafting reaction is 0.26 time of the weight of the sorghum stalk biomass particles;
2) preparing composite modified hectorite:
(1) quaternization of hectorite: placing 100g of hectorite with the granularity of less than 200 meshes in an aqueous solution of octadecyl dimethyl benzyl ammonium chloride, and performing ultrasonic dispersion for 48 hours to obtain a quaternary ammonium salinized hectorite dispersion liquid; 0.15g octadecyl dimethyl benzyl ammonium chloride per gram hectorite is required;
(2) complexation of hectorite: adding ethylenediamine into the hectorite dispersion liquid, wherein each gram of hectorite needs 0.08g of ethylenediamine for complexing, stirring for 12 hours at 40 ℃, then filtering until filtrate is free of chloride ions detected by silver nitrate, and drying at 70 ℃ to obtain composite modified hectorite;
(3) preparing inorganic material hybridized porous biomass microspheres:
placing 10g of composite modified hectorite and 8g of glycine grafted biomass into 100ml of ethanol water solution, uniformly stirring, adding 0.1g of triethylamine, then adding 0.4g of cross-linking agent glutaraldehyde, carrying out reflux reaction for 2 hours, filtering, washing with water, and drying at 65 ℃ to constant weight to obtain the inorganic material hybridized porous biomass microspheres.
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