CN110272085B - Modified blue algae biochar composite material and application thereof in treatment of electroplating wastewater - Google Patents
Modified blue algae biochar composite material and application thereof in treatment of electroplating wastewater Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C02F1/722—Oxidation by peroxides
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Abstract
The invention discloses a modified blue algae biochar composite material and application thereof in treatment of electroplating wastewater, and belongs to the technical field of biochar composite material preparation. Drying, grinding and sieving the lake Taihu blue algae, mixing the lake Taihu blue algae with an activating agent, and thermally cracking to obtain modified blue algae biochar; and soaking the modified blue algae biochar in an iron-containing solution, and further modifying to obtain the modified blue algae biochar composite material. The modified blue algae biochar composite material prepared by the invention has the adsorption and catalysis capabilities, and when the composite material is used for treating electroplating wastewater, metal ions in the wastewater can be efficiently removed through adsorption and Fenton-like reaction. And the composite material has strong stability and can be repeatedly used.
Description
Technical Field
The invention relates to a modified blue algae biochar composite material, a preparation method thereof and application thereof in treating electroplating wastewater, and belongs to the technical field of biochar composite material preparation.
Background
In recent years, the aerospace, automotive, jewelry and other industries have rapidly developed, and thus the demand for durable metallic materials and related processes has been increasing. Electroplating is an indispensable link in the production process of durable metal materials, and the attractiveness and the performance of the materials can be greatly improved through electroplating treatment. In 2015, the electroplating industry at home and abroad accounts for about 37% of the total market share of the metal surface treatment industry. Accordingly, approximately billionths of cubic meters of electroplating wastewater is generated each year. The electroplating wastewater contains heavy metals such as copper, chromium, nickel, zinc and the like and various organic pollutants. Among them, the zinc-nickel alloy can endow the metal material with excellent mechanical strength and corrosion resistance, so the zinc-nickel alloy is one of the most important plating species in the electroplating industry. Meanwhile, organic reagents such as complexing agents, antistatic agents, cosolvents, brightening agents and the like are used in the zinc-nickel alloy electroplating process to improve the electroplating quality, so that metal ions in the zinc-nickel alloy electroplating wastewater are in a complexing state, ordinary chemical precipitation cannot remove the metal ions in the complexing state, and the treatment difficulty of the zinc-nickel alloy electroplating wastewater is greatly improved. If the waste water is not deeply treated, the waste water is directly discharged, and heavy metal ions in the electroplating waste water are enriched through the food chain net, so that the safety of an ecological system and the health of human beings are harmed.
At present, methods for treating electroplating wastewater include adsorption, precipitation, flocculation, flotation, ion exchange, membrane treatment and the like, wherein adsorption and precipitation are preferred due to low cost investment and high treatment efficiency. However, some electroplating wastewater containing a complexing agent cannot be treated by simple adsorption or precipitation. If the transition metal can be loaded on the adsorbing material, the transition metal can catalyze hydrogen peroxide to generate hydroxyl free radicals (OH) in the presence of hydrogen peroxide, so that Advanced Oxidation (AOP) is generated; through advanced oxidation, organic pollutants such as a complexing agent and the like can be degraded to release the complexing metal, so that the complexing metal is changed into the ionic metal, and the removal of heavy metals is facilitated.
The biochar is a material with high carbon content formed by thermally cracking biomass under an anaerobic or anoxic condition, generally has high specific surface area and rich oxygen-containing functional groups, so the biochar has strong adsorption capacity and is widely applied to soil remediation. Due to the characteristic of strong specific adsorption capacity of the biochar, the biochar can be used as a matrix to load other materials to obtain a biochar composite material, and further can be used for treating wastewater.
Patent (CN 108455603A) discloses a mesoporous-rich biochar and a preparation method thereof, which is to carbonize wood chips, bamboo powder, walnut shells or straws in an inert gas atmosphere to obtain the mesoporous-rich biochar. However, this method yielded biochar with a specific surface area of 569m 2 Per g, pore volume 0.194cm 3 /g。
The patent (201810177711.4) discloses a preparation method of a biochar-based negative composite material, wherein orange peel powder and urea solution are mixed, stirred, freeze-dried and then mixed with rectorite powder and calcined, and the prepared biochar composite material is good in stability and large in adsorption capacity. However, the composite material has only an adsorption capacity, and does not have a catalytic capacity.
Blue algae, as a kind of freshwater algae, is widely distributed all over the world, and point source pollution of recent industrial sewage and non-point source pollution of agricultural fertilizers cause higher nitrogen and phosphorus concentration of water bodies, thereby causing excessive growth of the freshwater algae and formation of water bloom. The blue algae outbreak can destroy the ecological environment of the local water body and threaten the drinking water safety of residents in the basin. For example, in China, the quantity of blue algae salvaged in the Taihu basin in 2018 reaches 186 million tons all the year round. Therefore, the blue algae is urgently utilized as resources. At present, the method for treating the blue algae is mainly salvaged, the salvaged blue algae is less in resource utilization, and the prior art is mainly used for anaerobic fermentation. The patent (CN 102618585A) discloses a method for producing hydrogen by utilizing anaerobic fermentation of bloom-forming cyanobacteria, which is characterized in that the salvaged and collected cyanobacteria is filled in a closed container for induced hydrogen production, clean energy is generated, and waste can be changed into valuable. However, the anaerobic reaction causes problems such as odor and anaerobic sludge. Therefore, a method for more cleanly utilizing the blue algae resources is to be developed.
Disclosure of Invention
[ problem ] to
The method aims to treat the high-difficulty electroplating wastewater of the zinc-nickel alloy electroplating wastewater and provide a new way for the resource utilization of the blue algae.
[ solution ]
The invention provides a preparation method of a modified blue algae biochar composite material, and the obtained biochar composite material has the advantages of large specific surface area, strong adsorption capacity, good stability, adsorption capacity and catalytic capacity, and can generate synergistic effects of adsorption and Fenton-like oxidation in the presence of hydrogen peroxide.
The preparation method of the modified blue algae biochar composite material comprises the following steps:
(1) Mixing the blue algae which is dried and ground and then passes through a sieve of 80-100 meshes with an activating agent;
(2) Carrying out thermal cracking treatment on the mixed sample obtained in the step (1) in an inert atmosphere;
(3) Grinding the sample subjected to the thermal cracking treatment in the step (2), sieving the ground sample with a sieve of 80-100 meshes, then carrying out acid washing and water washing until the pH value is neutral, and drying the sample;
(4) Soaking the sample dried in the step (3) in an iron-containing solution, adjusting alkali, depositing, drying and roasting;
(5) And (4) washing and filtering the sample roasted in the step (4), collecting a solid part and drying to obtain the modified blue algae biochar composite material.
In one embodiment of the invention, the cyanobacteria in step (1) are all taken from Taihu lake.
In one embodiment of the invention, the drying temperature in the step (1) is 80-120 ℃, and the drying time is 12-24 h; the sieving treatment refers to sieving through a sieve of 80 to 100 meshes.
In one embodiment of the invention, in the step (1), the activating agent is one of potassium hydroxide, zinc chloride and potassium hydrogen phosphate, and the mass ratio of the blue algae to the activating agent is (0.5-1): 1.
In one embodiment of the present invention, the inert gas in the step (2) is nitrogen, and the flow rate of the inert gas is 60 to 100sccm.
In one embodiment of the present invention, the thermal cracking in step (2) is divided into two stages, wherein the thermal cracking temperature of the first stage is 200-400 ℃, and the thermal cracking time is 60-90 min; the second stage thermal cracking temperature is 600-800 deg.c and the thermal cracking time is 60-120 min.
In one embodiment of the invention, the acid used for pickling in the step (3) is dilute hydrochloric acid, and the concentration of the dilute hydrochloric acid is 0.1-1 mol/L; the drying temperature is 80-120 ℃ and the drying time is 12-24 h.
In one embodiment of the present invention, the iron-containing solution in step (4) is one of ferric chloride and ferric nitrate, and the mass ratio of iron in the solution to the sample (charcoal) dried in step (3) is (0.05-0.2): 1; the reagent for adjusting alkali is ammonia water solution, the concentration is 10-20 wt%; the roasting device is a muffle furnace, the temperature is 200-400 ℃, and the time is 2-4h.
In one embodiment of the invention, the drying in step (5) is vacuum drying at 60-85 ℃ for 12-24 h.
The invention also provides a method for treating electroplating wastewater by applying the prepared modified blue algae biochar composite material, the modified blue algae biochar composite material is added into the electroplating wastewater, hydrogen peroxide is added for fenton-like oxidation reaction after adsorption balance is carried out, alkali is added for precipitation after the reaction is finished, supernatant is effluent, and the modified blue algae biochar composite material is recycled after desorption and cleaning.
In one embodiment of the invention, before the modified blue algae biochar composite is added into the electroplating wastewater, the pH value of the electroplating wastewater is adjusted to 2-8.
In one embodiment of the invention, the adding amount of the modified blue algae biochar composite material is 0.5-5 g/L of wastewater.
In one embodiment of the invention, the adsorption equilibration time is 20min.
In one embodiment of the invention, the addition amount of hydrogen peroxide is 5-30 mmol, and the Fenton reaction time is 60min.
In one embodiment of the invention, the modified cyanobacteria biochar composite can be recycled at least 4 times.
[ advantageous effects ]
On one hand, the invention takes the waste biomass blue algae as a raw material, and carries out staged thermal cracking under the condition of adding an activating agent, so that the pyrolyzed biochar has huge specific surface area, and the adsorption capacity of the blue algae biochar is improved. The blue algae is rich in organic matters and has high carbon content. The ash content of the biochar obtained after pyrolysis is less, the blue algae has relatively smaller molecular weight, and the granularity of the biochar after pyrolysis is far smaller than that of biochar such as straws and the like.
On the other hand, after the blue algae biochar is loaded with ferric oxide, the modified blue algae biochar composite material is prepared, and the composite material has excellent adsorption capacity and catalytic capacity. In the presence of hydrogen peroxide, fenton-like reaction occurs, and iron oxide can catalyze the hydrogen peroxide to generate hydroxyl free radicals, so that the degradation of organic pollutants is realized. Therefore, the modified blue algae biochar composite material can efficiently remove heavy metals in electroplating wastewater containing complexing agents through adsorption and Fenton-like reaction, and can be recycled.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of modified cyanobacterial biochar obtained in example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the modified cyanobacteria biochar composite obtained in example 2.
FIG. 3 is the X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) patterns of the modified cyanobacterial biochar and the modified cyanobacterial biochar composite in example 3.
FIG. 4 is a diagram of the recycling treatment effect of the modified blue algae biochar composite.
FIG. 5 is a comparison graph of the effects of different biochar composites on treating electroplating wastewater; ● : the blue algae biochar is not activated, namely the blue algae biochar obtained after the step of mixing with potassium hydroxide in the step (1) is omitted on the basis of the embodiment 1; a tangle-solidup: straw biochar composite, namely the straw biochar composite prepared in comparative example 1;
modified cyanobacteria biochar, i.e., the modified cyanobacteria biochar prepared in example 1;
a modified blue algae biochar composite material, namely the modified blue algae biochar composite material prepared in the embodiment 2; ■ : iron oxide powder, i.e. the same amount of iron as in example 2.
Detailed Description
The detection method of the nickel content in the wastewater comprises the following steps: the method for detecting the concentration of metal ions in the wastewater adopts a flame atomic absorption photometry, a water sample is filtered by a 0.45 mu m water system filter membrane and then is tested, the used instrument is a flame atomic absorption spectrometer (AAF-7000F), and the concentration of the metal ions in the water sample is accurately obtained by the instrument according to a set standard curve.
Example 1 preparation of modified cyanobacterial biochar without iron Loading
A preparation method of modified blue algae biochar comprises the following steps:
(1) Drying the blue algae in the Taihu lake in an oven at 105 ℃ for 24 hours, grinding after drying, sieving by a 80-mesh sieve, and mixing a sieved sample with potassium hydroxide, wherein the mass ratio of the sample to the potassium hydroxide is 1;
(2) Under the protection of nitrogen with the gas flow rate of 80sscm, carrying out thermal cracking on the mixed sample, wherein the thermal cracking process is divided into two stages, firstly heating to 400 ℃ at the speed of 5 ℃/min, carrying out thermal cracking for 90min at the temperature of 400 ℃, then heating to 800 ℃ at the speed of 10 ℃/min, and carrying out heat preservation for 2h at the temperature of 800 ℃;
(3) And (3) grinding the thermally cracked sample in a mortar, sieving with a 100-mesh sieve, then pickling in 1mol/L hydrochloric acid, washing with water to be neutral, placing in a drying oven, and drying the sample at 105 ℃ to obtain the modified cyanobacteria biochar.
FIG. 1 is a Scanning Electron Microscope (SEM) image of the modified cyanobacterial biochar obtained in example 1. The specific surface area and pore volume of the modified cyanobacteria biochar material prepared in the example 1 are shown in table 1. The modified blue algae biochar has rich pore canal structures and large specific surface area, thereby improving the adsorption capacity and being beneficial to compounding with other materials.
Example 2 preparation of iron-loaded modified cyanobacteria biochar composite
A preparation method of a modified blue algae biochar composite material comprises the following steps:
(1) Drying the blue algae in the Taihu lake in an oven at 105 ℃ for 24 hours, grinding after drying, and sieving by a 80-mesh sieve. Then mixing the sieved sample with potassium hydroxide, wherein the mass ratio of the sample to the potassium hydroxide is 1;
(2) Thermally cracking the mixed sample under the protection of nitrogen with the gas flow rate of 80sscm, wherein the thermal cracking process is divided into two stages, namely, firstly heating to 400 ℃ at the speed of 5 ℃/min, thermally cracking for 90min at the temperature of 400 ℃, then heating to 800 ℃ at the speed of 10 ℃/min, and keeping the temperature at 800 ℃ for 2h;
(3) Grinding the thermally cracked sample in a mortar, sieving the ground sample by a 100-mesh sieve, then pickling the ground sample in 1mol/L hydrochloric acid, washing the ground sample with water until the pH value is =7, placing the washed sample in an oven, and drying the sample at 105 ℃;
(4) Soaking the dried sample in a ferric nitrate solution for 8 hours, wherein the mass ratio of iron to carbon in the solution is 0.2;
(5) And (3) washing the roasted sample with water, filtering, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the modified blue algae biochar composite.
The specific surface area and pore volume of the biochar composite prepared in example 2 are shown in table 1. FIG. 2 is a Scanning Electron Microscope (SEM) image of the modified cyanobacteria biochar composite obtained in example 2, and it can be seen that the surface of the composite becomes relatively rough. Further, as shown in fig. 3, the X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) both showed peaks of iron oxide, which together showed that iron oxide was successfully complexed with cyanobacterial biochar.
Example 3 example of treatment of electroplating wastewater
The materials prepared in the above examples 1 and 2 are used for treating zinc-nickel alloy electroplating wastewater. The parameters of the plating waste water are shown in Table 2.
The specific treatment process comprises the following steps: firstly, adjusting the initial pH value of electroplating wastewater to 6, then adding 0.5g of modified blue algae biochar or modified blue algae biochar composite material, adding 30mmol of hydrogen peroxide to perform Fenton-like oxidation reaction after 20min of adsorption balance is achieved, adding sodium hydroxide to precipitate after the reaction is finished (about 60 min), filtering supernatant through a 0.45 mu m filter head, measuring the concentration of nickel ions by using a flame atomic absorption method, and desorbing and cleaning the modified blue algae biochar composite material for recycling. The formula for calculating the nickel removal rate is shown in the following formula (1).
In the formula: eta- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -nickel removal rate (%)
C 0 Initial concentration of nickel (mg/L) in the plating waste water without treatment
C t Concentration of treated nickel(mg/L)
FIG. 5 is a graph showing the treatment effect of electroplating wastewater, wherein the modified blue algae biochar shows excellent adsorption capacity, and can adsorb 69.8% of nickel according to the formula (1), but can not completely remove the nickel in the electroplating wastewater; the modified blue algae biochar composite material prepared by compounding with ferric oxide can efficiently remove heavy metals in water through the synergistic effect of adsorption and Fenton-like reaction, and the removal rate is up to 99.1% according to the calculation of the formula (1).
In addition, taking iron oxide powder to treat the electroplating wastewater. The treatment conditions were as follows: adjusting the pH value of the zinc-nickel alloy wastewater to about 3, adding iron oxide powder for adsorption for 20min, adding hydrogen peroxide, reacting for 60min, adding sodium hydroxide for precipitation, collecting the supernatant after precipitation, filtering with a 0.45-micrometer filter membrane, and measuring the metal ion concentration by a flame atomic absorption method. The amount of iron oxide used was the same as the iron content of the biochar composite in example 2. As shown in fig. 5, the removal rate of nickel by iron oxide in the adsorption stage was 8.23% and the removal rate of nickel after fenton-like reaction was 74.01%, calculated according to the formula (1).
Therefore, the zinc-nickel alloy electroplating wastewater can not be deeply treated by the adsorption of the single blue algae biochar or the Fenton-like reaction generated by catalyzing hydrogen peroxide by the single iron oxide, and the zinc-nickel alloy electroplating wastewater can be efficiently treated by the modified blue algae biochar composite material through coupling the adsorption and the Fenton-like reaction.
After the zinc-nickel alloy electroplating wastewater is treated, collecting the modified blue algae biochar composite material, cleaning with an alkali solution (0.1 mol/L sodium hydroxide solution), cleaning with deionized water until the pH value is neutral, and finally drying in an oven for 12 hours. The zinc-nickel alloy electroplating wastewater was treated again in the same manner as above. Fig. 4 is a recovery graph of the modified blue algae biochar composite material, and the removal rate of nickel can still reach 93.7% after 4 times of recycling, which shows that the composite material has better stability.
Table 1: examples preparation of samples specific surface area and pore volume
| Sample (I) | Specific surface area (m) 2 /g) | Total pore volume (cm) 3 /g) | Average pore diameter (nm) |
| Unmodified cyanobacteria biochar | 17.9 | 0.0235 | 4.281 |
| Modified blue algae biochar | 1657.8 | 0.9559 | 2.306 |
| Modified blue algae biochar composite material | 1256.5 | 0.5662 | 2.137 |
| Comparative example | 569 | 0.399 | 2.81 |
Table 2: various indexes of electroplating wastewater
| Index (es) | pH | COD(mg/L) | Ni(mg/L) | Conductivity (ms/S) |
| Measured value | 11.78 | 524.16 | 2.818 | 1.32 |
Comparative example 1
The method comprises the steps of (1) taking corn straw biochar produced by Nanjing Zhi-Hui-Tech Co., ltd as a raw material, and carrying out iron loading by adopting the methods recorded in the steps (4) and (5) in the embodiment 2 to obtain the straw biochar composite material. The same zinc-nickel alloy electroplating wastewater was treated with the straw biochar composite material by the process described in example 3. As shown in fig. 5, in the adsorption stage, the removal rate of nickel was calculated to be 23.99% according to the formula (1), and after the fenton-like reaction, the removal rate of nickel was calculated to be 47.92% according to the formula (1).
Comparative example 2
On the basis of the example 2, the mass ratios of the iron and carbon in the step (4) are respectively adjusted to be 0.05. The modified blue algae composite materials are treated by the same process as that in the embodiment 3. As shown in table 3, the removal rates of nickel were 86.28%, 90.61%, and 99.14%, respectively, as calculated according to the formula (1) after the adsorption-coupling fenton-like reaction was completed. Therefore, different iron loads have different nickel removal rates, and the iron load with the appropriate concentration can efficiently remove nickel in the wastewater.
Table 3: removal rate of composite materials prepared by different iron-carbon ratios to nickel
| Iron to carbon ratio | Nickel removal Rate (%) |
| 0.05:1 | 86.28 |
| 0.1:1 | 90.61 |
| 0.2:1 | 99.14 |
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by one skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The application of the modified blue algae biochar composite material in nickel removal of zinc-nickel alloy electroplating wastewater is characterized in that the modified blue algae biochar composite material is added into the zinc-nickel alloy electroplating wastewater, and after adsorption balance is achieved, hydrogen peroxide is added to carry out fenton-like oxidation reaction;
the preparation method of the modified blue algae biochar composite material comprises the following steps:
(1) Mixing the blue algae which is dried and ground and then sieved by a sieve with 80 to 100 meshes with an activating agent; wherein the activating agent is potassium hydroxide, and the mass ratio of the blue algae to the activating agent is (0.5-1) to 1;
(2) Carrying out thermal cracking treatment on the mixed sample obtained in the step (1) in an inert atmosphere, wherein the thermal cracking treatment is divided into two stages, the thermal cracking temperature of the first stage is 200-400 ℃, and the thermal cracking time is 60-90 min; the second-stage thermal cracking temperature is 600 to 800 ℃, and the thermal cracking time is 60 to 120 min;
(3) Grinding the sample subjected to the thermal cracking treatment in the step (2), sieving the ground sample through a sieve of 80-100 meshes, then carrying out acid washing and water washing until the pH value is neutral, and drying the sample;
(4) Soaking the sample dried in the step (3) in an iron-containing solution, adjusting alkali, depositing, drying and roasting; wherein the iron-containing solution is one of ferric chloride solution or ferric nitrate solution, and the mass ratio of iron in the solution to the dried sample carbon in the step (3) is (0.05-0.2): 1; the reagent for adjusting alkali is ammonia water solution, and the concentration is 10 to 20wt%; the roasting device is a muffle furnace, the temperature is 200 to 400 ℃, and the time is 2 to 4 hours;
(5) And (4) washing and filtering the sample roasted in the step (4), collecting a solid part and drying to obtain the modified blue algae biochar composite material.
2. The application of the paint as claimed in claim 1, wherein the drying temperature in the step (1) is 80 to 120 ℃, and the drying time is 12 to 24h; the screening treatment is to pass through a sieve with 80 to 100 meshes.
3. The use according to claim 1, wherein the inert gas in step (2) is nitrogen, and the flow rate of the inert gas is 60 to 100sccm.
4. The use of claim 1, wherein in the step (3), the acid for pickling is dilute hydrochloric acid, and the concentration of the dilute hydrochloric acid is 0.1 to 1mol/L; the drying temperature is 80 to 120 ℃, and the time is 12 to 24h.
5. The application of claim 1, wherein the preparation method of the modified cyanobacteria biochar composite comprises the following steps:
(1) Drying the blue algae in the Taihu lake in an oven at 105 ℃ for 24 hours, grinding after drying, and sieving with a 80-mesh sieve; then mixing the sieved sample with potassium hydroxide, wherein the mass ratio of the sieved sample to the potassium hydroxide is 1;
(2) Thermally cracking the mixed sample under the protection of nitrogen with the gas flow rate of 80sscm, wherein the thermal cracking process is divided into two stages, namely, firstly heating to 400 ℃ at the speed of 5 ℃/min, thermally cracking for 90min at the temperature of 400 ℃, then heating to 800 ℃ at the speed of 10 ℃/min, and keeping the temperature at 800 ℃ for 2h;
(3) Grinding the thermally cracked sample in a mortar, sieving the ground sample with a 100-mesh sieve, then carrying out acid washing in 1mol/L hydrochloric acid, washing with water until the pH value is =7, placing the sample in an oven, and drying the sample at 105 ℃;
(4) Soaking the dried sample in a ferric nitrate solution for 8 hours, wherein the mass ratio of iron to carbon in the ferric nitrate solution is 0.2;
(5) And (3) washing the roasted sample with water, filtering, and drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the modified blue algae biochar composite material.
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| CN110272085B (en) * | 2019-07-30 | 2023-02-24 | 江南大学 | Modified blue algae biochar composite material and application thereof in treatment of electroplating wastewater |
| CN110787771A (en) * | 2019-10-25 | 2020-02-14 | 天津大学 | Modified blue algae biochar and preparation method and application thereof |
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