CN113336335B - Nano material for industrial and chemical sewage treatment and preparation method thereof - Google Patents
Nano material for industrial and chemical sewage treatment and preparation method thereof Download PDFInfo
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Abstract
The invention provides a nano material for industrial and chemical sewage treatment and a preparation method thereof. The nano material can quickly remove heavy metals in chemical wastewater, so that the wastewater discharge reaches the discharge standard, and the application prospect is good.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a nano material for industrial and chemical sewage treatment and a preparation method thereof.
Background
Water is an indispensable resource in human development and survival and is directly related to human survival, but with the increase of population base number and the acceleration of social urbanization and industrialization process, the occupation amount of water resources per capita is sharply reduced, the water pollution problem is aggravated, and the human survival is seriously threatened. The causes of water pollution include many aspects, including organoleptic pollution, organic pollution, inorganic pollution (including heavy metal pollution), biological pollution, etc.
For example, in the whole production process from mining, ore dressing, smelting to product processing, enterprises producing non-ferrous metals discharge wastewater containing heavy metal elements such as antimony, copper, lead, zinc, arsenic, chromium and the like, and in addition, industries such as electroplating, pigment, electronics, instruments and the like can cause serious heavy metal pollution.
Heavy metal is a typical accumulated pollutant, has the characteristics of accumulation, nondegradation and high toxicity, can be biologically absorbed and enriched along with a food chain, and finally accumulates in a human body to cause the hazards of chronic poisoning and the like. The most typical examples are osteodynia caused by Cd pollution and water caused by Hg, and cancer caused by Hg, Cd, As and Pb pollution. Since heavy metal pollution causes serious harm to the ecological environment and human health, many domestic and foreign scholars have developed many techniques for treating heavy metals one after another.
The sewage containing heavy metals is usually high in acidity, the types of heavy metal ions are complex, and the heavy metal ions exist in various valence states and forms, so that the treatment difficulty is extremely high. The current common heavy metal wastewater treatment method comprises the following steps: neutralization precipitation method, sulfide precipitation method, ferrite method, adsorption method, ion exchange method, biological method (bioflocculation method, phytoremediation method, animal remediation method) and the like, there are many problems that are common, such as: the natural flocculation sedimentation takes longer time, the discharged water is difficult to reach the national discharge standard, and the like, the heavy metal recovery cannot be realized to achieve the effect of exhausting the resources, or the treatment efficiency is low, the treatment cost is high, and the like.
The adsorption method has the advantages of wide source of adsorption materials, large adsorption capacity, high adsorption speed, high removal efficiency, simple and convenient operation, repeated regeneration and recycling and the like, so that the adsorption method is generally concerned by people. However, the prior commercially available adsorbent has poor stability and insufficient adsorption capacity, and has large dosage and higher treatment cost when being applied to heavy metal sewage treatment
Patent CN105692771B discloses a heavy metal sewage treatment material, which is prepared by using hydrochloric acid modified sepiolite, pyridine quaternary ammonium salt type cationic polyacrylamide, zeolite powder, modified attapulgite, cellulose xanthate, chitosan, crosslinked carboxymethyl starch, hydroxypropyl cellulose graft copolymer, ferric sulfate, lime powder, activated carbon powder and the like as raw materials, and the material is simply piled up with some existing porous materials, and has limited synergy, limited maximum adsorption capacity and long treatment time.
Disclosure of Invention
The invention aims to provide a nano material for chemical wastewater treatment and a preparation method thereof, which can quickly remove heavy metals in wastewater.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of a nano material for treating heavy metal ions in chemical wastewater comprises the steps of firstly loading ferrous sulfate on the surface of a layered titanate nano material to prepare an intermediate product, then crosslinking the intermediate product and a cationic polymer under the action of sodium tripolyphosphate, and adding coated bacterial powder in the crosslinking process to obtain the nano material; wherein the coating bacterium powder is obtained by coating Arthrobacter mexicanus and Micrococcus luteus; the cationic polymer is obtained by modifying branched polyethyleneimine with trifluoroacetic anhydride.
Preferably, the preparation method of the layered titanate nano-material comprises the following steps: firstly, 1 part of isopropyl titanate is dispersed in 10-12 parts of 8-10 mol/L sodium hydroxide solution by ultrasonic waves, then the mixture is transferred to a hydrothermal reaction kettle, hydrothermal reaction is carried out for 18-22 hours at the temperature of 150-180 ℃, and the layered titanate nano material is obtained by filtering, washing with deionized water and drying.
Preferably, the preparation method of the intermediate product comprises the following steps in parts by weight: firstly, dispersing 1 part of layered titanate nano material in 6-9 parts of deionized water by ultrasonic waves, introducing nitrogen, adding 8-10 parts of ferrous sulfate aqueous solution with the mass concentration of 30-40%, uniformly stirring, then dropwise adding 4-5 parts of sodium sulfide aqueous solution with the mass concentration of 20-30% to react to generate ferrous sulfide, continuously introducing nitrogen for 15-20 minutes after dropwise adding is finished, and sealing and standing for 20-22 hours to obtain the intermediate product.
More preferably, the flow of the nitrogen is 90-110 mL/min.
Preferably, the preparation method of the nano material comprises the following steps of: dispersing 1 part of intermediate product in 8-10 parts of deionized water by ultrasonic waves, adjusting the pH value to 4.6-5.0, adding 0.5-0.7 part of cationic polymer while stirring, uniformly stirring, then adding 5-8 parts of sodium tripolyphosphate aqueous solution with the mass concentration of 20-30%, stirring for 6-9 minutes at 28-32 ℃, adding 0.05-0.08 part of coated bacterial powder, stirring for 10-15 minutes at 28-32 ℃, centrifuging, taking precipitate, washing and drying to obtain the nano material.
Preferably, the preparation method of the coated bacterial powder comprises the following steps in parts by weight: adding 1 part of Arthrobacter mexicanus and 0.3-0.5 part of Micrococcus luteus into 5-7 parts of sodium alginate aqueous solution with mass concentration of 30-40%, uniformly stirring to obtain mixed solution, adding the mixed solution into 8-10 parts of calcium chloride aqueous solution with mass concentration of 2-3% while stirring, standing for 8-10 hours, centrifuging to obtain precipitate, and thus obtaining the coated bacterium powder.
Preferably, the preparation method of the cationic polymer comprises the following steps in parts by weight: firstly, adding 1 part of branched polyethyleneimine into 8-10 parts of deionized water, then slowly dropwise adding 0.3-0.5 part of trifluoroacetic anhydride while stirring, continuously stirring for reacting for 35-40 hours after dropwise adding is finished, dialyzing, and freeze-drying to obtain the cationic polymer.
Further preferably, the slow dropping time is 30-40 minutes.
The invention also claims a nano material for treating heavy metal ions in chemical wastewater, which is obtained by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the invention, ferrous sulfate is loaded on the surface of a layered titanate nano material to prepare an intermediate product, then the intermediate product is crosslinked with a cationic polymer under the action of sodium tripolyphosphate, and coating bacteria powder is added in the crosslinking process to obtain the nano material for treating heavy metal ions in sewage, so that the heavy metal in the sewage can be quickly removed;
(2) the coated bacterium powder is obtained by coating the Arthrobacter misolae and the Micrococcus luteus, and has a certain adsorption effect on heavy metals probably due to irregular protrusions on the surface of a strain and aggregation of precipitates, and in addition, metabolites also have a certain adsorption effect on heavy metal ions. The two strains of the Arthrobacter mexicanus and the Micrococcus luteus have different extracellular conditions and different metabolites, and the two strains synergistically enhance the adsorption effect on heavy metal ions;
(3) the cationic polymer is obtained by modifying branched polyethyleneimine with trifluoroacetic anhydride, wherein the branched polyethyleneimine has a chelation effect on heavy metal ions, and forms hydrogen bonds after being modified with the trifluoroacetic anhydride, so that a three-dimensional network structure is constructed, pores are enriched, and the adsorption effect is enhanced;
(4) the layered titanate nano material has the advantages of nano particle size, large specific surface area and good adsorption effect on heavy metal ions, and the specific surface area is further increased after ferrous sulfate is loaded on the surface of the layered titanate nano material, so that the adsorption effect is enhanced. Under the action of sodium tripolyphosphate, the intermediate product is crosslinked with a cationic polymer to form more pores, and the coating bacterium powder is added in the crosslinking process to be coated in the pores, so that the coating bacterium powder plays a role in protection, and a certain buffer growth time is provided for the strain, so that the strain is prevented from being killed in a high-concentration heavy metal ion environment, and the adsorption effect is prevented from being influenced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The branched polyethyleneimine related to the invention is purchased from Shanghai Beinuo Biotechnology Co., Ltd; mcsolbacter mexicana, CGMCC1.15895, deposited in China general microbiological culture Collection center by Xiamen university in 2016, 9, 20 days; micrococcus luteus, CGMCC1.9051, is deposited in China center for culture Collection of microorganisms in 2009, 1 month and 19 days of Chengdu biological research institute of Chinese academy of sciences.
Example 1
A preparation method of a nano material for treating heavy metal ions in chemical wastewater comprises the steps of firstly loading ferrous sulfate on the surface of a layered titanate nano material to prepare an intermediate product, then crosslinking the intermediate product and a cationic polymer under the action of sodium tripolyphosphate, and adding coated bacterial powder in the crosslinking process to obtain the nano material; wherein the coating bacterium powder is obtained by coating Arthrobacter mexicanus and Micrococcus luteus; the cationic polymer is obtained by modifying branched polyethyleneimine with trifluoroacetic anhydride.
Wherein the preparation method of the layered titanate nano material comprises the following steps: firstly, dispersing 10g isopropyl titanate in 100g 10mol/L sodium hydroxide solution by ultrasonic wave, then transferring the solution to a hydrothermal reaction kettle, carrying out hydrothermal reaction for 22 hours at 150 ℃, filtering, washing with deionized water, and drying to obtain the layered titanate nano material.
The preparation method of the intermediate product comprises the following steps: firstly, dispersing 10g of layered titanate nano material in 60g of deionized water by ultrasonic waves, introducing nitrogen, adding 100g of ferrous sulfate aqueous solution with the mass concentration of 30%, uniformly stirring, dropwise adding 50g of sodium sulfide aqueous solution with the mass concentration of 20% to react to generate ferrous sulfide, continuously introducing nitrogen for 20 minutes after dropwise adding, sealing and standing for 20 hours to obtain the intermediate product. The nitrogen flow is 110 mL/min.
The preparation method of the nano material comprises the following steps: firstly, dispersing 10g of intermediate product in 80g of deionized water by ultrasonic waves, adjusting the pH value to 5.0, adding 5g of cationic polymer while stirring, uniformly stirring, then adding 80g of sodium tripolyphosphate aqueous solution with the mass concentration of 20%, stirring for 6 minutes at 32 ℃, adding 0.8g of coated bacterium powder, stirring for 15 minutes at 28 ℃, centrifuging to obtain a precipitate, washing and drying to obtain the nano material.
The preparation method of the coated bacterium powder comprises the following steps: firstly, adding 10g of Arthrobacter mexicanus and 3g of Micrococcus luteus into 70g of sodium alginate aqueous solution with the mass concentration of 30%, uniformly stirring to obtain mixed solution, then adding the mixed solution into 100g of calcium chloride aqueous solution with the mass concentration of 2% while stirring, standing for 10 hours, centrifuging and taking precipitate to obtain the coated bacterium powder.
The preparation method of the cationic polymer comprises the following steps: firstly, adding 10g of branched polyethyleneimine into 80g of deionized water, then slowly dropwise adding 5g of trifluoroacetic anhydride while stirring, continuously stirring for reacting for 35 hours after dropwise adding is finished, dialyzing, and freeze-drying to obtain the cationic polymer. The slow addition time was 40 minutes.
Example 2
A preparation method of a nano material for treating heavy metal ions in chemical wastewater comprises the steps of firstly loading ferrous sulfate on the surface of a layered titanate nano material to prepare an intermediate product, then crosslinking the intermediate product and a cationic polymer under the action of sodium tripolyphosphate, and adding coated bacterial powder in the crosslinking process to obtain the nano material; wherein the coating bacterium powder is obtained by coating Arthrobacter mexicanus and Micrococcus luteus; the cationic polymer is obtained by modifying branched polyethyleneimine with trifluoroacetic anhydride.
Wherein the preparation method of the layered titanate nano material comprises the following steps: firstly, dispersing 10g of isopropyl titanate in 120g of 8mol/L sodium hydroxide solution by ultrasonic waves, then transferring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 18 hours, filtering, washing with deionized water, and drying to obtain the layered titanate nano material.
The preparation method of the intermediate product comprises the following steps: firstly, dispersing 10g of layered titanate nano material in 90g of deionized water by ultrasonic waves, introducing nitrogen, adding 80g of 40% ferrous sulfate aqueous solution by mass concentration, uniformly stirring, dropwise adding 40g of 30% sodium sulfide aqueous solution by mass concentration to react to generate ferrous sulfide, continuously introducing nitrogen for 15 minutes after the dropwise addition is finished, sealing and standing for 22 hours to obtain the intermediate product. The nitrogen flow is 90 mL/min.
The preparation method of the nano material comprises the following steps: firstly, dispersing 10g of intermediate product in 100g of deionized water by ultrasonic waves, adjusting the pH value to 4.6, adding 7g of cationic polymer while stirring, uniformly stirring, then adding 50g of 30% sodium tripolyphosphate aqueous solution, stirring for 9 minutes at 28 ℃, adding 0.5g of coated bacterium powder, stirring for 10 minutes at 32 ℃, centrifuging to obtain a precipitate, washing, and drying to obtain the nano material.
The preparation method of the coated bacterium powder comprises the following steps: firstly, adding 10g of Arthrobacter mexicanus and 5g of Micrococcus luteus into 50g of sodium alginate aqueous solution with the mass concentration of 40%, uniformly stirring to obtain mixed solution, then adding the mixed solution into 80g of calcium chloride aqueous solution with the mass concentration of 3% while stirring, standing for 8 hours, centrifuging and taking precipitate to obtain the coated bacterium powder.
The preparation method of the cationic polymer comprises the following steps: firstly, adding 10g of branched polyethyleneimine into 100g of deionized water, then slowly dropwise adding 3g of trifluoroacetic anhydride while stirring, continuously stirring for reacting for 40 hours after dropwise adding, dialyzing, and freeze-drying to obtain the cationic polymer. The slow addition time was 30 minutes.
Example 3
A preparation method of a nano material for treating heavy metal ions in chemical wastewater comprises the steps of firstly loading ferrous sulfate on the surface of a layered titanate nano material to prepare an intermediate product, then crosslinking the intermediate product and a cationic polymer under the action of sodium tripolyphosphate, and adding coated bacterial powder in the crosslinking process to obtain the nano material; wherein the coating bacterium powder is obtained by coating Arthrobacter mexicanus and Micrococcus luteus; the cationic polymer is obtained by modifying branched polyethyleneimine with trifluoroacetic anhydride.
Wherein the preparation method of the layered titanate nano material comprises the following steps: firstly, dispersing 10g of isopropyl titanate in 110g of 9mol/L sodium hydroxide solution by ultrasonic waves, then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 20 hours, filtering, washing with deionized water, and drying to obtain the layered titanate nano material.
The preparation method of the intermediate product comprises the following steps: firstly, dispersing 10g of layered titanate nano material in 80g of deionized water by ultrasonic waves, introducing nitrogen, adding 90g of 35% ferrous sulfate aqueous solution with mass concentration, uniformly stirring, dropwise adding 45g of 25% sodium sulfide aqueous solution with mass concentration to react to generate ferrous sulfide, continuously introducing nitrogen for 18 minutes after dropwise addition, sealing and standing for 21 hours to obtain the intermediate product. The nitrogen flow is 100 mL/min.
The preparation method of the nano material comprises the following steps: firstly, dispersing 10g of intermediate product in 90g of deionized water by ultrasonic waves, adjusting the pH value to 4.8, adding 6g of cationic polymer while stirring, uniformly stirring, then adding 70g of 25% sodium tripolyphosphate aqueous solution with the mass concentration, stirring for 8 minutes at 30 ℃, adding 0.7g of coated bacterium powder, stirring for 12 minutes at 30 ℃, centrifuging to obtain a precipitate, washing and drying to obtain the nano material.
The preparation method of the coated bacterium powder comprises the following steps: firstly, adding 10g of Arthrobacter mexicanus and 4g of Micrococcus luteus into 60g of sodium alginate aqueous solution with mass concentration of 35%, uniformly stirring to obtain mixed solution, then adding the mixed solution into 90g of calcium chloride aqueous solution with mass concentration of 2.5% while stirring, standing for 9 hours, centrifuging and taking precipitate to obtain the coated bacterium powder.
The preparation method of the cationic polymer comprises the following steps: firstly, adding 10g of branched polyethyleneimine into 90g of deionized water, then slowly dropwise adding 4g of trifluoroacetic anhydride while stirring, continuously stirring for reacting for 38 hours after dropwise adding, dialyzing, and freeze-drying to obtain the cationic polymer. The slow addition time was 35 minutes.
Comparative example 1
A preparation method of a nano material for treating heavy metal ions in chemical wastewater comprises the steps of firstly, crosslinking a layered titanate nano material and a cationic polymer under the action of sodium tripolyphosphate, and adding coated bacterial powder in the crosslinking process to obtain the nano material; wherein the coating bacterium powder is obtained by coating Arthrobacter mexicanus and Micrococcus luteus; the cationic polymer is obtained by modifying branched polyethyleneimine with trifluoroacetic anhydride.
Wherein the preparation method of the layered titanate nano material comprises the following steps: firstly, dispersing 10g isopropyl titanate in 100g 10mol/L sodium hydroxide solution by ultrasonic wave, then transferring the solution to a hydrothermal reaction kettle, carrying out hydrothermal reaction for 22 hours at 150 ℃, filtering, washing with deionized water, and drying to obtain the layered titanate nano material.
The preparation method of the nano material comprises the following steps: firstly, dispersing 10g of layered titanate nano material in 80g of deionized water by ultrasonic waves, adjusting the pH value to 5.0, adding 5g of cationic polymer while stirring, uniformly stirring, then adding 80g of sodium tripolyphosphate aqueous solution with the mass concentration of 20%, stirring for 6 minutes at 32 ℃, adding 0.8g of coated bacterium powder, stirring for 15 minutes at 28 ℃, centrifuging to obtain a precipitate, washing, and drying to obtain the nano material.
The preparation method of the coated bacterium powder comprises the following steps: firstly, adding 10g of Arthrobacter mexicanus and 3g of Micrococcus luteus into 70g of sodium alginate aqueous solution with the mass concentration of 30%, uniformly stirring to obtain mixed solution, then adding the mixed solution into 100g of calcium chloride aqueous solution with the mass concentration of 2% while stirring, standing for 10 hours, centrifuging and taking precipitate to obtain the coated bacterium powder.
The preparation method of the cationic polymer comprises the following steps: firstly, adding 10g of branched polyethyleneimine into 80g of deionized water, then slowly dropwise adding 5g of trifluoroacetic anhydride while stirring, continuously stirring for reacting for 35 hours after dropwise adding is finished, dialyzing, and freeze-drying to obtain the cationic polymer. The slow addition time was 40 minutes.
Comparative example 2
A preparation method of a nano material for treating heavy metal ions in chemical wastewater comprises the steps of loading ferrous sulfate on the surface of a layered titanate nano material to prepare an intermediate product, and then uniformly mixing the intermediate product with coated bacterial powder to obtain the nano material; wherein the coating bacterium powder is obtained by coating Arthrobacter mexicanus and Micrococcus luteus.
Wherein the preparation method of the layered titanate nano material comprises the following steps: firstly, dispersing 10g isopropyl titanate in 100g 10mol/L sodium hydroxide solution by ultrasonic wave, then transferring the solution to a hydrothermal reaction kettle, carrying out hydrothermal reaction for 22 hours at 150 ℃, filtering, washing with deionized water, and drying to obtain the layered titanate nano material.
The preparation method of the intermediate product comprises the following steps: firstly, dispersing 10g of layered titanate nano material in 60g of deionized water by ultrasonic waves, introducing nitrogen, adding 100g of ferrous sulfate aqueous solution with the mass concentration of 30%, uniformly stirring, dropwise adding 50g of sodium sulfide aqueous solution with the mass concentration of 20% to react to generate ferrous sulfide, continuously introducing nitrogen for 20 minutes after dropwise adding, sealing and standing for 20 hours to obtain the intermediate product. The nitrogen flow is 110 mL/min.
The preparation method of the coated bacterium powder comprises the following steps: firstly, adding 10g of Arthrobacter mexicanus and 3g of Micrococcus luteus into 70g of sodium alginate aqueous solution with the mass concentration of 30%, uniformly stirring to obtain mixed solution, then adding the mixed solution into 100g of calcium chloride aqueous solution with the mass concentration of 2% while stirring, standing for 10 hours, centrifuging and taking precipitate to obtain the coated bacterium powder.
Comparative example 3
A preparation method of a nano material for treating heavy metal ions in chemical wastewater comprises the steps of firstly loading ferrous sulfate on the surface of a layered titanate nano material to prepare an intermediate product, then crosslinking the intermediate product and a cationic polymer under the action of sodium tripolyphosphate, and adding coated bacterial powder in the crosslinking process to obtain the nano material; wherein the coating bacterium powder is obtained by coating Arthrobacter mexicanus; the cationic polymer is a branched polyethyleneimine.
Wherein the preparation method of the layered titanate nano material comprises the following steps: firstly, dispersing 10g isopropyl titanate in 100g 10mol/L sodium hydroxide solution by ultrasonic wave, then transferring the solution to a hydrothermal reaction kettle, carrying out hydrothermal reaction for 22 hours at 150 ℃, filtering, washing with deionized water, and drying to obtain the layered titanate nano material.
The preparation method of the intermediate product comprises the following steps: firstly, dispersing 10g of layered titanate nano material in 60g of deionized water by ultrasonic waves, introducing nitrogen, adding 100g of ferrous sulfate aqueous solution with the mass concentration of 30%, uniformly stirring, dropwise adding 50g of sodium sulfide aqueous solution with the mass concentration of 20% to react to generate ferrous sulfide, continuously introducing nitrogen for 20 minutes after dropwise adding, sealing and standing for 20 hours to obtain the intermediate product. The nitrogen flow is 110 mL/min.
The preparation method of the nano material comprises the following steps: firstly, dispersing 10g of intermediate product in 80g of deionized water by ultrasonic waves, adjusting the pH value to 5.0, adding 5g of cationic polymer while stirring, uniformly stirring, then adding 80g of sodium tripolyphosphate aqueous solution with the mass concentration of 20%, stirring for 6 minutes at 32 ℃, adding 0.80g of coated bacterium powder, stirring for 15 minutes at 28 ℃, centrifuging to obtain a precipitate, washing and drying to obtain the nano material.
The preparation method of the coated bacterium powder comprises the following steps: adding 10g of Arthrobacter mexicanus into 70g of sodium alginate aqueous solution with the mass concentration of 30%, uniformly stirring to obtain mixed solution, adding the mixed solution into 100g of calcium chloride aqueous solution with the mass concentration of 2% while stirring, standing for 10 hours, centrifuging and taking precipitate to obtain the coated bacterium powder.
The performance evaluation of the nano materials prepared in the examples and the comparative examples is specifically as follows:
1. comparing the adsorption effect of the nano material on heavy metal ions
Preparing As with initial concentration of 1200mg/L3+、Cr3+、Pb2+、Ni+The metal ion aqueous solution simulates chemical heavy metal sewage, and then the nano materials obtained in examples 1-3 and comparative examples 1-3 are respectively adopted for treatment (the mass volume ratio of the nano material to the heavy metal sewage is 1 g: 10L), and the treatment is finished (the temperature is 25 ℃, the treatment time is 30 minutes)) Then filtering to obtain filtrate, analyzing and detecting the concentration of metal ions in the filtrate and the heavy metal sewage before treatment by adopting a flame atomic absorption spectrophotometry, and further calculating the adsorption capacity of the nano material, namely the mass of the metal ions adsorbed by the nano material with unit mass, wherein the result is shown in table 1.
TABLE 1 comparison of adsorption amounts
| As3+Adsorption Capacity (mg/g) | Cr3+Adsorption Capacity (mg/g) | Pb2+Adsorption Capacity (mg/g) | Ni+Adsorption Capacity (mg/g) | |
| Example 1 | 338 | 340 | 371 | 309 |
| Example 2 | 352 | 361 | 364 | 291 |
| Example 3 | 343 | 347 | 368 | 315 |
| Comparative example 1 | 302 | 300 | 286 | 267 |
| Comparative example 2 | 229 | 201 | 217 | 200 |
| Comparative example 3 | 268 | 243 | 235 | 242 |
As can be seen from Table 1, the nanomaterials of examples 1 to 3 can realize As-control in 30 minutes3+、Cr3+、Pb2+、Ni+And (3) effectively removing the heavy metal ions.
The intermediate product is replaced by the layered titanate nano material in the comparative example 1, the coated bacterium powder in the comparative example 2 is directly mixed with the intermediate product, the coated bacterium powder in the comparative example 3 is obtained by coating the Arthrobacter misonii, the cationic polymer is branched polyethyleneimine, the adsorption effect of the obtained nano material on heavy metal ions is obviously poor, the two strains synergistically promote the improvement of the adsorption effect, the surface modification and the crosslinking function are beneficial to improving the specific surface area and the porosity, and further the adsorption effect of the heavy metal ions is improved.
2. The nano materials prepared in examples 1 to 3 and comparative examples 1 to 3 were applied to the treatment of wastewater
Taking the wastewater of a certain metallurgical chemical industry factory as an example, the water inlet quality condition is as follows: the Chemical Oxygen Demand (COD) concentration is 4296mg/L, the total metal ion (including heavy metal ions such as arsenic, chromium and the like) content is 23500mg/L, the nano materials of examples 1-3 and comparative examples 1-3 are respectively adopted for treatment (the temperature is 25 ℃, the treatment time is 30 minutes), and the water quality condition of effluent is shown in Table 2. Wherein, the content of metal ions before treatment is detected by an EDTA complexation titration method, and the content of metal ions after treatment is determined by an atomic absorption spectrometry method.
TABLE 2 Water quality Condition
| COD(mg/L) | Total metal ion content (mg/L) | |
| Example 1 | 72 | 10 |
| Example 2 | 47 | 8 |
| Example 3 | 65 | 15 |
| Comparative example 1 | 454 | 258 |
| Comparative example 2 | 1069 | 985 |
| Comparative example 3 | 877 | 733 |
As can be seen from Table 2, the nano materials of the embodiments 1 to 3 can effectively reduce the COD and the metal ion content, and the effluent quality is far superior to that of the comparative examples 1 to 3.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation method of a nano material for industrial and chemical sewage treatment is characterized in that ferrous sulfate is loaded on the surface of a layered titanate nano material to prepare an intermediate product, then the intermediate product is crosslinked with a cationic polymer under the action of sodium tripolyphosphate, and coated bacterial powder is added in the crosslinking process to obtain the nano material; wherein the coating bacterium powder is obtained by coating Arthrobacter mexicanus and Micrococcus luteus; the cationic polymer is obtained by modifying branched polyethyleneimine with trifluoroacetic anhydride;
the preparation method of the intermediate product comprises the following steps: firstly, ultrasonically dispersing 1 part of layered titanate nano material in 6-9 parts of deionized water, introducing nitrogen, adding 8-10 parts of ferrous sulfate aqueous solution with the mass concentration of 30-40%, uniformly stirring, dropwise adding 4-5 parts of sodium sulfide aqueous solution with the mass concentration of 20-30% to react to generate ferrous sulfide, continuously introducing nitrogen for 15-20 minutes after dropwise addition is finished, and hermetically standing for 20-22 hours to obtain an intermediate product;
the preparation method of the nano material comprises the following steps: dispersing 1 part of intermediate product in 8-10 parts of deionized water by ultrasonic waves, adjusting the pH value to 4.6-5.0, adding 0.5-0.7 part of cationic polymer while stirring, uniformly stirring, then adding 5-8 parts of sodium tripolyphosphate aqueous solution with the mass concentration of 20-30%, stirring for 6-9 minutes at 28-32 ℃, adding 0.05-0.08 part of coated bacterial powder, stirring for 10-15 minutes at 28-32 ℃, centrifuging, taking precipitate, washing and drying to obtain the nano material.
2. The preparation method of claim 1, wherein the layered titanate nano-material is prepared by the following steps in parts by weight: firstly, 1 part of isopropyl titanate is dispersed in 10-12 parts of 8-10 mol/L sodium hydroxide solution by ultrasonic waves, then the mixture is transferred to a hydrothermal reaction kettle, hydrothermal reaction is carried out for 18-22 hours at the temperature of 150-180 ℃, and the layered titanate nano material is obtained by filtering, washing with deionized water and drying.
3. The preparation method according to claim 1, wherein the flow rate of the introduced nitrogen gas is 90 to 110 mL/min.
4. The preparation method of claim 1, wherein the coated fungal powder is prepared by the following steps in parts by weight: adding 1 part of Arthrobacter mexicanus and 0.3-0.5 part of Micrococcus luteus into 5-7 parts of sodium alginate aqueous solution with mass concentration of 30-40%, uniformly stirring to obtain mixed solution, adding the mixed solution into 8-10 parts of calcium chloride aqueous solution with mass concentration of 2-3% while stirring, standing for 8-10 hours, centrifuging to obtain precipitate, and thus obtaining the coated bacterium powder.
5. The method according to claim 1, wherein the cationic polymer is prepared by the following method in parts by weight: firstly, adding 1 part of branched polyethyleneimine into 8-10 parts of deionized water, then slowly dropwise adding 0.3-0.5 part of trifluoroacetic anhydride while stirring, continuously stirring for reacting for 35-40 hours after dropwise adding is finished, dialyzing, and freeze-drying to obtain the cationic polymer.
6. The method according to claim 5, wherein the slow dropping time is 30 to 40 minutes.
7. A nano material for industrial and chemical sewage treatment prepared by the preparation method of any one of claims 1 to 6.
8. The application of the nano material of claim 7 in treating heavy metal ions in chemical wastewater.
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| CN103272552A (en) * | 2013-05-08 | 2013-09-04 | 上海交通大学 | Recyclable titanate nanometer material capable of treating waste water and application method thereof |
| CN108772044A (en) * | 2018-07-06 | 2018-11-09 | 福建师范大学福清分校 | Chitosan loaded sheath bacteria composite biological adsorption of magnetic Nano and preparation method thereof |
| CN111558365A (en) * | 2020-06-03 | 2020-08-21 | 朱晴 | Nano material for treating heavy metal ions in sewage and preparation method thereof |
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| CN103272552A (en) * | 2013-05-08 | 2013-09-04 | 上海交通大学 | Recyclable titanate nanometer material capable of treating waste water and application method thereof |
| CN108772044A (en) * | 2018-07-06 | 2018-11-09 | 福建师范大学福清分校 | Chitosan loaded sheath bacteria composite biological adsorption of magnetic Nano and preparation method thereof |
| CN111558365A (en) * | 2020-06-03 | 2020-08-21 | 朱晴 | Nano material for treating heavy metal ions in sewage and preparation method thereof |
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