CN114477357A - Method for removing heavy metal in acidic waste liquid - Google Patents
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- CN114477357A CN114477357A CN202210041915.1A CN202210041915A CN114477357A CN 114477357 A CN114477357 A CN 114477357A CN 202210041915 A CN202210041915 A CN 202210041915A CN 114477357 A CN114477357 A CN 114477357A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4856—Proteins, DNA
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention belongs to the technical field of water treatment, and discloses a method for removing heavy metals in acidic waste liquid, which comprises the following steps: mixing the modified keratin fibers with the acidic waste liquid to remove heavy metals in the acidic waste liquid; the modified keratin fiber is prepared by subjecting keratin fiber to 0.2-0.8 mol.L‑1And soaking in an alkali solution for 4-10 hours, and then modifying by sulfydryl.The modified keratin fiber is applied to the strongly acidic waste liquid to remove heavy metals, so that the problem of poor removal effect caused by heavy metal desorption is avoided in the removal process, alkali neutralization of the waste liquid is not needed, and the problem of alkali consumption is avoided.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for removing heavy metals in acidic waste liquid.
Background
With the coming of relevant environmental protection policies, the monitoring strength of society and relevant units on heavy metals in the environment is increased. Environmental laboratories and chemical laboratories in enterprises, universities and scientific research institutions can generate a large amount of heavy metal waste liquid due to analysis and detection of a large amount of samples. If the waste liquid is directly discharged into a sewer without being treated, the generated environmental pollution is not negligible. Related environmental monitoring units and colleges do not have matched waste liquid treatment equipment, and the cost of outsourcing to a special waste liquid treatment company is high.
At present, the treatment technology of the wastewater containing heavy metal ions can be classified into the following four technologies: conventional methods, physical treatment methods, chemical treatment methods, biological treatment methods. More specifically, the treatment methods applied in various water treatment fields include extraction, flotation, membrane filtration, ion exchange, electrodialysis, electrochemistry, adsorption and biological treatment methods, and specifically include the following steps:
1.1 extraction method
The extraction method is a relatively common physical and chemical method, and various heavy metal ion waste liquids can be basically treated by the extraction method. However, in the extraction process by adopting the traditional heavy metal solvent, the pretreatment wastes time and labor, the consumption of the organic solvent is large, the regeneration is difficult, and secondary pollution is easily caused if the post-treatment is not properly operated.
1.2 flotation method
The flotation method utilizes the adsorption of bubbles to perform solid-liquid separation. The flotation method for treating the heavy metal ion waste liquid is a new technology, and can achieve the dual purposes of eliminating pollution and recycling metal by controlling conditions. In addition, flotation can also make up for the deficiencies of membrane filtration in the treatment of certain metal hydroxides and carbonates. Compared with other methods, the flotation method has the characteristics of simple equipment, small occupied area, convenient start-stop, suitability for intermittent production and the like.
1.3 Membrane filtration method
The membrane filtration method comprises a reverse osmosis method and an ultrafiltration method, and the technical core of the method is a membrane with a selective permeation function, and the solid-liquid separation is realized by utilizing the interception function of the membrane. The reverse osmosis method applies higher pressure to the wastewater containing heavy metal ions, so that water in the solution permeates through the special semipermeable membrane and heavy metal ion solutes are difficult to permeate, and further the wastewater is concentrated. The polymer enhanced ultrafiltration method can effectively intercept the polymer macromolecules combined with heavy metal ions by the ultrafiltration membrane. Therefore, different water-soluble polymers can be used for selectively separating heavy metal ions at low energy consumption through different polymer functional groups.
The method has the advantages of low investment, small occupied area and easy operation, can realize the enrichment of heavy metal ions, and is beneficial to the recovery of recyclable materials. At present, the reverse osmosis method is mainly used for treating nickel plating and copper plating wastewater.
1.4 ion exchange method
The ion exchange method is mainly used for treating the wastewater by utilizing the selective exchange effect of ion exchange on anions and cations in the wastewater. The method has wide application range, and almost all inorganic harmful ions can be treated by an ion exchange method. The treated wastewater can be used as plating solution make-up water or cleaning water. If the treatment of the regenerated eluent is not considered, the 'zero discharge system' without waste water discharge can be realized by adopting an ion exchange method.
However, the method has high one-time investment, large occupied area, low concentration of pollutants in the wastewater and poor resistance to water quality change. In practical application, the method is suitable for being combined with evaporation concentration, reverse osmosis, electrodialysis and other methods to achieve better treatment effect.
1.5 electrodialysis method
Like charges repel and opposite charges attract. When low-voltage direct current is applied to the wastewater, anions move to the anode, cations move to the cathode and selectively permeate the anion and the cation membranes, so that the electrolyte is concentrated in certain areas, and purer water is obtained in other areas. However, when the electrodialysis method is used, the concentration of the electrolyte in the wastewater containing heavy metal ions cannot be too low, otherwise, sufficient conductivity cannot be ensured, and the dialysis efficiency is reduced. By using electrodialysis method, the concentration ratio of concentrated solution to diluted solution can reach about 100 times, which is higher than that of reverse osmosis method, and the concentrated solution can be reused in plating bath. This method requires attention to prevent clogging of the membrane, and thus requires strict filtration of the feed water to remove solid impurities.
1.6 electrochemical method
The electrochemical method decomposes, oxidizes, reduces, and precipitates toxic substances in wastewater by using an electrochemical reaction between a cathode and an anode when power is applied. The method has the advantages that: the equipment is relatively simple, one electrolytic cell can have multiple functions of oxidation, reduction, condensation, floating and the like, and is easy to automatically control; the electrons are used as a reactant, so that secondary pollution can be avoided. The application of electrochemical methods to environmental pollution control has become a research field of great attention. The latest research result is the three-dimensional electrode method. The three-dimensional electrode is formed by filling granular or chip-shaped materials between electrodes of a traditional two-dimensional electrolytic cell, charging the surfaces of the granular or chip-shaped materials, and performing electrochemical reaction on the surfaces of the granular or chip-shaped materials. Compared with the traditional two-dimensional electrode, the area ratio of the electrolytic cell can be increased, the material migration speed is improved, a supporting electrolyte is not required to be added, so that the occurrence of side reactions and environmental pollution are avoided, the product separation is easy, the internal resistance of the system is lower, the energy utilization rate is high, and a new way is opened up for treating a wastewater treatment system with low conductivity, low intrinsic kinetic speed or small limiting diffusion current. The three-dimensional electrode has the disadvantage of uneven current potential distribution in the bed, which may lead to local "dead zones" or side reactions. But generally, the prospect of treating the heavy metal ion wastewater by adopting the three-dimensional electrode is very wide.
1.7 biological treatment
The biological treatment method is to enrich heavy metal ions in a body through metabolism of microorganisms, and then achieve the purpose of removing pollutants through discharge of residual activated sludge, but because the microorganisms cannot metabolize the metal ions, the biological treatment method only carries out one-step migration movement to transfer the heavy metal ions from a solution to the sludge. Because of the advantages of less sludge generation, more types of microorganisms participating in purification reaction, long survival time, strong adaptability to the change of the water quality and the water quantity of the wastewater, simple and convenient operation and the like, the biofilm method is the mainstream of the research field of the biological treatment of the wastewater containing the heavy metal ions. The biofilm method attaches microbial cells on a solid carrier to grow and breed, and film-shaped biological sludge is formed on the solid carrier. The method has the disadvantages that because dead cells have no metabolic capability, the treatment potential of microorganisms cannot be improved through genetic engineering, the valence of metal ions cannot be changed in the adsorption process, the toxicity of heavy metal ions is reduced, and secondary pollution is caused if sludge is not treated properly.
1.8 adsorption method
The adsorption method is used for adsorbing and removing toxic and harmful substances in the wastewater by utilizing the effects of physical adsorption, chemical adsorption, oxidation reduction and the like of the adsorbent. Some adsorbents have porous morphological structures and further have large surface areas; some adsorbents have-NH2And functional groups such as-C-O-, -COOH, -OH, and-SH-, and an electron cloud of these functional groups can adsorb an electron cloud of the metal cation.
Several decontamination techniques such as membrane systems, precipitation, ion exchange resins, electrodialysis, etc. are still very expensive. The adsorption material for removing the heavy metal in the water has a very good application prospect, and the main reason is that the adsorption material not only can efficiently remove the heavy metal, but also has relatively low price. The struggle against heavy metal pollution has stimulated the exploration of eco-friendly technologies, and cheaper and more effective natural biosorbents have been extensively studied as potential adsorbents for heavy metals, such as iris, black chickpea shells, orange peel, coffee peel, sugar beet pectin gel, red eucalyptus bark, sugar cane bagasse, plants of the apiaceae family (parsley, coriander and coriander), and the like.
At present, the waste phenomenon of hair resources is serious, and a large amount of hair is discarded as garbage. Only by taking wool as an example, a large amount of thick and long wool is wasted due to low quality and high processing difficulty every year. Thus, if a suitable and viable process could be developed, these protein wastes could be converted into utilizable resources, which on the one hand would protect the environment and on the other hand would turn it into wealth.
It has long been known that human hair has a strong heavy metal adsorption capacity for a number of reasons. First, there are minute cracks on the surface of human hair, which can promote the physical adsorption of heavy metal ions to the hair surface. Second, the long peptide chains in hair contain unshared pairs of electrons in atoms such as oxygen and nitrogen. These electron pairs can coordinate with heavy metal ions, thereby promoting chemisorption of these ions on the hair surface. Finally, the modified human hair has higher proportion of sulfydryl and can be strongly coordinated with heavy metal ions, so that the chemical adsorption to the hair is enhanced.
In the prior art, an adsorbent is generally applied to adsorb heavy metals in weak acid or neutral waste liquid, and after adsorption, the adsorbent adsorbing the heavy metals is washed, soaked and the like by using strong acid so as to desorb the heavy metals in the adsorbent, so that the adsorbent can be recycled. However, the purpose of recycling by using strong acid also reflects that the heavy metal adsorbed by the adsorbent is easy to desorb in a strong acid environment, and the product in the prior art is not suitable for removing the heavy metal in a strong acid waste liquid. In the case of strongly acidic waste liquid, the common technique is to add alkali to neutralize and precipitate heavy metals in the waste liquid, which requires a large amount of alkali.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a method for removing heavy metals in acidic waste liquid, which can avoid the problem that the heavy metals cannot be effectively removed due to the fact that the heavy metals are desorbed from an adsorbent in the strong acidic waste liquid, and does not need to carry out alkali neutralization on the waste liquid.
Specifically, the invention relates to the following technical scheme:
a method for removing heavy metals in acidic waste liquid comprises the following steps: mixing the modified keratin fibers with acidic waste liquid to remove heavy metals in the acidic waste liquid; the modified keratin fiber is prepared by subjecting keratin fiber to 0.2-0.8 mol.L-1Soaking in an alkali solution for 4-10 hours, and then modifying by sulfydryl.
The adsorption removal of heavy metals in waste liquid by adopting an adsorbent is a common wastewater treatment method, and at present, more adsorbents are generally applied to weak acid or neutral waste liquid for removing heavy metals. However, after the adsorbent adsorbs heavy metals, the heavy metals are easily desorbed from the more acidic solution. The inventor finds in research that the modified keratin fiber subjected to the specific treatment of the invention is difficult to elute by using a strong acid solution after adsorbing heavy metals, namely, the modified keratin fiber is difficult to desorb in an acid solution after adsorbing heavy metals, so that the modified keratin fiber can be applied to a strong acid waste liquid to remove heavy metals, and the problem of poor removal effect caused by heavy metal desorption in the removal process is avoided. At the same time, the user can select the desired position,
in some examples of the invention, the pH of the acidic waste liquid is less than 4, preferably less than or equal to 3.5, more preferably less than or equal to 3, and even more preferably 0 to 2.
In some examples of the invention, the keratin fibers include at least one of human hair, animal hair (e.g., wool, silk, etc.), preferably hair with a high disulfide bond content.
In some embodiments of the invention, the modified keratin fibers are prepared by a process comprising: 0.2 to 0.8 mol.L is used-1And soaking the keratin fibers in the aqueous alkali for 4-10 hours, and then reacting with mercaptoethanol to obtain the modified keratin fibers.
In some examples of the invention, the alkali solution is a strong alkali solution, including at least one of a NaOH solution, a KOH solution, preferably a NaOH solution.
In some embodiments of the invention, the ratio of keratin fibers to alkali solution is 1g: 300-600 mL.
In some embodiments of the invention, the time period for soaking in the alkaline solution is 4 to 12 hours, preferably about 6 hours.
In some embodiments of the invention, the ratio of keratin fibers to mercaptoethanol is 1g: 0.5-1.5 mL.
In some embodiments of the invention, the time for the reaction with mercaptoethanol is 4 to 10 hours, preferably 4 to 8 hours, and more preferably about 6 hours.
In some embodiments of the invention, the system for reacting with mercaptoethanol further comprises urea (CO (NH)2)2). In practice, the keratin fibers can be soaked in an alkaline solution and then washed to be neutralMixing with urea solution.
In some embodiments of the invention, the urea solution has a concentration of 3 to 5 mol.L-1. The ratio of the keratin fibers to the urea solution is 1g: 30-60 mL.
In some embodiments of the invention, the method further comprises the step of washing the material to neutrality after the reaction with mercaptoethanol is completed.
In some examples of the present invention, the temperature during the soaking in the alkali solution and the reaction with mercaptoethanol is independently 0 to 40 ℃, preferably 10 to 30 ℃, and more preferably at room temperature.
In some examples of the invention, the mixing ratio of the modified keratin fibers and the acidic waste liquid is 0.1g: 20-30 mL, preferably 0.1g:25 mL.
In some examples of the invention, the temperature for removing the heavy metal in the acidic waste liquid is 0-40 ℃, preferably 10-30 ℃, and more preferably at room temperature; the time is 0.5-40 h.
In some embodiments of the present invention, the method further comprises the steps of mixing the modified keratin fibers with an acidic waste solution to remove heavy metals from the acidic waste solution: removing the modified keratin fibers from the acidic waste liquid, and desorbing the modified keratin fibers by using a desorbent. Through the operation, the heavy metal adsorbed by the modified keratin fiber can be desorbed, so that the modified keratin fiber can be recycled for the second time.
In some examples of the invention, the desorbent comprises EDTA, Na2At least one of EDTA. The modified keratin fiber of the present invention is difficult to desorb under acidic conditions, and therefore, the desorption cannot be performed by a common acid washing method, but EDTA or Na is used2The EDTA can desorb the heavy metal adsorbed by the modified keratin fiber, and the desorption rate reaches more than 70 percent.
In some examples of the invention, the desorption process is in particular: the modified keratin fibers are mixed with a desorbent solution to effect desorption. The concentration of the desorbent solution is 0.05-0.2 mol.L-1Preferably 0.1 mol. L-1. Desorption agent solution and method for adsorbing heavy metalThe proportion of the sexual keratin is 200-300 mL: 1 g. The desorption temperature is 0-40 ℃, preferably 20-30 ℃, and more preferably at room temperature; the time is 2-7 h, preferably 5-7 h, and more preferably 6-7 h.
In some examples of the invention, the heavy metal comprises at least one of copper (II), zinc (II), cadmium (II), chromium (III), nickel (II), lead (II), preferably lead (II).
In some examples of the invention, the concentration of heavy metal in the acidic waste liquid is 0-500 mg-L-1。
In some embodiments of the invention, the acidic waste stream is derived from a chemical laboratory waste stream, an iron and steel plant acidic waste stream, a chemical plant acidic waste stream, a dye plant acidic waste stream, an electroplating plant acidic waste stream, or a mine acidic waste stream.
Compared with the prior art, the invention has the following beneficial effects:
the invention applies the modified keratin fiber to the strongly acidic waste liquid to remove heavy metals, and avoids the problem of poor removal effect caused by heavy metal desorption in the removal process.
Drawings
FIG. 1 is a surface microstructure of hair before and after modification;
FIG. 2 is an XPS analysis of hair before and after modification;
FIG. 3 is a graph showing the adsorption of different metal ions by modified hair;
FIG. 4 shows Pb for modified hair2+The elution rate.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are conventional in the art.
Example 1
The preparation method of the modified hair comprises the following steps: taking natural black human hair with the thickness of more than or equal to 10 cm, cleaning attached dirt with a cleaning agent, thoroughly washing with deionized water, and finally drying in an air oven at 40 ℃. Weigh out about 10g of dry hair and place in500mL of 0.5 mol. L was added to a 1L beaker-1NaOH solution, soaking for 6 hours, until the solution turns dark brown, the human hair turns brown and loses part of elasticity. Taking out, and washing hair to be neutral by using deionized water. To minimize the loss of treated hair, the pre-treated hair was placed in a clean beaker and 500mL of 4 mol. L was added-1CO(NH2)2Then 10mL of beta-mercaptoethanol (. beta. -Me) was added. And (3) placing the hair in a fume hood for 6 hours, taking out the hair, washing the hair to be neutral by using deionized water, and drying the hair in an oven at the temperature of 40 ℃ to obtain the modified hair.
And (3) testing structure and performance:
the microstructure of the surface of the hair before (A) and after (B) modification is shown in FIG. 1. The untreated hair surface is very smooth, while the pretreated hair surface has many cracks which increase the surface area of the hair, and the cracks help the β -ME to enter the hair and break one disulfide bond into two-SH groups. XPS analysis of hair before and after modification is shown in FIG. 2. Figure 2 shows that β -Me treatment increases the proportion of-SH on the hair surface, which will increase the hair's chemisorption capacity.
0.1g of modified hair was added to 25mL of metal ion (Pb) at room temperature2+、Cu2+、Zn2+、Cd2+、Cr2+And Ni2+) The mixture was left to stand for 6 hours in the presence of a solution (pH 3.43). All heavy metal ions have the same molar initial concentration (C)0＝1mmol·L-1). The adsorption amounts of the modified hair to the respective metal ions are shown in fig. 3. The result shows that the adsorption order of the modified hair to each metal ion is sequentially Pb2+、Cu2+、Ni2+、Cr2+To Zn2+、Cd2+The adsorption is very slight, which shows that the modified hair has adsorption selectivity to heavy metals.
0.1g of modified hair was collected at room temperature (25 ℃ C.), and 25mL of the modified hair was added thereto at a pH of 3.43 and 500 mg. multidot.L-1Pb2+Standing in the aqueous solution for 24 hr to obtain the product with adsorbed Pb2+Modified hair of (1), wherein Pb2+The removal rate was 35%. Then, 0.1g of the thus-obtained mixture was allowed to adsorb Pb2+Is immersed in 25mL of hydrochloric acid solution having pH of 1 or 2After 24h of soaking, Pb2+Desorption rates in strong hydrochloric acid solutions of both pH values<5 percent. It can be seen that the modified hair adsorbs Pb2+Later, desorption is not easy under more acidic conditions.
0.1g of the thus-obtained mixture was adsorbed with Pb2+The modified hair was left in a 25mL portion of a 0.1 mol. L solution-1Na of (2)2Pb in EDTA solution at different times2+The elution rate of (2) is shown in FIG. 4. FIG. 4 shows that Na2EDTA can make Pb2+When the hair is desorbed from the modified hair, the elution rate reaches 78 percent after 5 hours.
Will elute Pb2+Adding the modified hair with 25mL of pH 3.43, 500 mg.L-1Pb of2+In the aqueous solution, after standing for 24 hours, Pb is tested2+The removal rate is 30 percent; continuing the same procedure for elution and then eluting Pb again2+Adding new 25mL of Pb with pH 3.43 and 300ppm2+In the aqueous solution, after standing for 24 hours, Pb is tested2+The removal rate was 13%. It can be seen that Na is used2After EDTA is eluted, the modified hair also has certain Pb2+The adsorption performance, however, gradually decreases as the number of cycles increases.
Comparative example 1
The comparative example differs from example 1 in that the hair was not modified and was applied directly to absorb Pb2+And a desorption test was performed.
Specifically, 10 cm long or longer hairs were mixed together, the attached dirt was washed with a detergent, thoroughly rinsed with deionized water, and finally dried in an air oven at 40 ℃. 0.1g of unmodified hair was collected at room temperature (25 ℃ C.), and 25mL of 1 mmol/L hair having a pH of 3.43 was added-1Pb2+Soaking in water solution for 6 hr to obtain Pb in hair2+The removal rate was 15%.
Comparative example 2
This comparative example differs from example 1 in that: parameters in the process of modifying hair are changed into weak base soaking, and then sulfhydrylation is carried out.
The modification method is 10 cm long or longerThe hair was mixed together, the adherent dirt was washed with detergent, rinsed thoroughly with deionized water and finally dried in an air oven at 40 ℃. For each experiment, about 10g of dry hair was weighed out and placed in a 1L beaker to which 500mL of 0.5 mol.L was added-1Na2CO3Soaking the solution for 6 hr until the solution turns black brown, and the human hair turns brown and loses partial elasticity, taking out, washing the hair with deionized water to neutrality, placing the pretreated hair in a clean beaker, adding 500mL of 4 mol.L-1CO(NH2)2Then, 10mL of beta-mercaptoethanol (. beta. -Me) was added. Standing in a fume hood for 6 hr, taking out, washing hair with deionized water to neutrality, and oven drying at 40 deg.C.
0.1g of modified hair was collected at room temperature (25 ℃ C.), and 25mL of the modified hair was added thereto at a pH of 3.43500 mg.L-1Pb2+Standing in the aqueous solution for 24 hr to obtain the product with adsorbed Pb2+Modified hair of (1), wherein Pb2+The removal rate was 9%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for removing heavy metals in acidic waste liquid is characterized by comprising the following steps: the method comprises the following steps: mixing the modified keratin fibers with acidic waste liquid to remove heavy metals in the acidic waste liquid; the modified keratin fiber is prepared by subjecting keratin fiber to 0.2-0.8 mol.L-1Soaking in an alkali solution for 4-10 hours, and then modifying by sulfydryl.
2. The method for removing heavy metals in acidic waste liquid according to claim 1, wherein: the pH value of the strong acid waste liquid is less than 4.
3. The method for removing heavy metals in acidic waste liquid according to claim 2, wherein: the pH value of the strong acid waste liquid is less than or equal to 3.5.
4. The method for removing heavy metals in acidic waste liquid according to claim 3, wherein: the pH value of the strong acid waste liquid is less than or equal to 3.
5. The method for removing heavy metals in acidic waste liquid according to claim 1, wherein: the keratin fiber comprises at least one of human hair and animal hair.
6. The method for removing heavy metals in acidic waste liquid according to claim 1, wherein: the preparation method of the modified keratin fiber comprises the following steps: 0.2 to 0.8 mol.L is used-1And soaking the keratin fibers in the aqueous alkali for 4-10 hours, and then reacting with mercaptoethanol to obtain the modified keratin fibers.
7. The method for removing heavy metals in acidic waste liquid according to claim 1, wherein: mixing the modified keratin fiber with a strongly acidic waste liquid, and removing heavy metals in the acidic waste liquid, the method further comprises the following steps: removing the modified keratin fibers from the acidic waste liquid, and desorbing the modified keratin fibers by using a desorbent.
8. The method for removing heavy metals in acidic waste liquid according to claim 7, wherein: the desorbent comprises EDTA and Na2At least one of EDTA.
9. The method for removing heavy metals in acidic waste liquid according to claim 7, wherein: the desorption process is specifically as follows: mixing the modified keratin fibers with a desorbent solution to perform desorption, wherein the desorbent solution has a concentration of 0.05-0.2 mol.L-1。
10. The method for removing heavy metals in acidic waste liquid according to claim 1, wherein: the heavy metal comprises at least one of copper (II), zinc (II), cadmium (II), chromium (III), nickel (II) and lead (II).
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