CN114314777A - Magnetic microsphere embedded with heavy metal capture agent, and preparation method and application thereof - Google Patents
Magnetic microsphere embedded with heavy metal capture agent, and preparation method and application thereof Download PDFInfo
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- CN114314777A CN114314777A CN202111668133.2A CN202111668133A CN114314777A CN 114314777 A CN114314777 A CN 114314777A CN 202111668133 A CN202111668133 A CN 202111668133A CN 114314777 A CN114314777 A CN 114314777A
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- Water Treatment By Sorption (AREA)
Abstract
The invention provides a magnetic microsphere containing a heavy metal trapping agent, which is obtained by complexing and crosslinking alginate and calcium ions; the magnetic microspheres have a polymer network structure formed after complexing and crosslinking; the magnetic microspheres comprise heavy metal capture agent and Fe3O4. According to the invention, the alginate with good biocompatibility is used for embedding and fixing the heavy metal capture agent and the magnetic particles, so that the heavy metal capture agent is prevented from remaining in the water body, secondary pollution to the water body is basically avoided, the resource recovery of heavy metal is synchronously realized, and the environment and economic benefits are good; and Fe is embedded and fixed in the magnetic microspheres3O4The magnetic particles improve the adsorption performance and solid-liquid separation efficiency of heavy metals, and are beneficial to the application of the magnetic particles in the field of sewage treatment. The magnetic microsphere provided by the invention has the advantages of good treatment effect, wide raw material source, low cost, low toxicity and high degreeDegradability and the like.
Description
Technical Field
The invention belongs to the technical field of metal wastewater treatment, relates to a magnetic microsphere containing a heavy metal capture agent, and a preparation method and application thereof, and particularly relates to a magnetic microsphere embedded with a heavy metal capture agent, and a preparation method and application thereof.
Background
With the rapid development of industrial production and urban modernization, the discharge of heavy metal wastewater brings serious harm to the environment and human health, and water pollution caused by heavy metals becomes a global problem. In order to meet the increasingly strict requirements of the national heavy metal wastewater discharge standard and the increasing attention of people on environmental protection, the existing wastewater treatment technology has been faced with serious challenges.
At present, a plurality of methods for treating heavy metal wastewater, such as a chemical precipitation method, an electrochemical method, a membrane separation method, an ion exchange method and the like, have the defects of high investment cost, high operating cost, easy generation of secondary pollution, non-ideal heavy metal removal effect and the like; secondly, due to the influences of high toxicity, durability, non-biodegradability, bioaccumulation and the like of the heavy metal capture agent, a conversion substance such as hydrogen sulfide generated in the reaction process of the heavy metal capture agent has a chemical structure similar to that of a biological metabolism substance, both the conversion substance and the biological metabolism substance can be combined with an active site of an enzyme at an active center of the enzyme, and the competition of the conversion substance and the biological metabolism substance can inhibit the formation of an intermediate product, reduce the catalytic reaction rate of the enzyme, and cause the problems of back-end biochemical inhibition and the like; meanwhile, in order to eliminate the risk and harm of heavy metals to the environment, the problems that the high-efficiency treatment and the heavy metal resource utilization of heavy metal wastewater are difficult to realize exist.
Therefore, how to search for a new heavy metal wastewater treatment method and research and develop an efficient heavy metal wastewater treatment agent has become a current research focus, and is one of the focuses of many research and development manufacturers and first-line researchers.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a magnetic microsphere containing a heavy metal capture agent, a preparation method and an application thereof, and particularly to a magnetic microsphere embedding a heavy metal capture agent. And the production process is simple and easy to control, and is favorable for realizing industrial scale production and application.
The invention provides a magnetic microsphere containing a heavy metal trapping agent, which is obtained by complexing and crosslinking alginate and calcium ions;
the magnetic microspheres have a polymer network structure formed after complexing and crosslinking;
the magnetic microspheres comprise heavy metal capture agent and Fe3O4。
Preferably, the magnetic microspheres have a mesh structure with pores inside;
the heavy metal scavenger is embedded in the polymeric network structure;
said Fe3O4Including Fe3O4A nanoparticle;
said Fe3O4Nanoparticles are embedded in the polymeric network structure.
Preferably, the heavy metal scavenger is complexed to the Fe3O4On the nanoparticles;
said Fe3O4The particle size of the nanoparticles is 10-40 nm.
The alginate accounts for 40-60% of the magnetic microspheres by mass;
the heavy metal trapping agent comprises one or more of organic nitrogen-containing heavy metal trapping agents, organic sulfur-containing heavy metal trapping agents and natural modified high-molecular heavy metal trapping agents;
the mass ratio of the heavy metal capture agent to the magnetic microspheres is 15-25%;
preferably, said Fe3O45-10% of the magnetic microspheres by mass;
the magnetic microspheres are embedded with heavy metal capture agents;
the magnetic microspheres are used for adsorbing heavy metals in the wastewater;
the magnetic microspheres are magnetic microspheres with a function of quickly separating the magnetic microspheres from wastewater.
Preferably, the particle size of the magnetic microspheres is 1000-4000 micrometers;
the magnetic microspheres have a porous structure;
the aperture of the magnetic microsphere is 10-100 mu m;
the porosity of the magnetic microspheres is 80-96%;
the specific surface area of the magnetic microspheres is 60-90 m2/g。
The invention provides a preparation method of a magnetic microsphere containing a heavy metal trapping agent, which comprises the following steps:
1) mixing the heavy metal catching agent solution and the alginate solution, adding ferroferric oxide, and continuously mixing to obtain a mixed solution;
2) and (3) dropping the mixed solution obtained in the step into a low-temperature calcium source solution by adopting a liquid drop method, and obtaining the magnetic microspheres after crosslinking and solidification and then freeze polymerization.
Preferably, the concentration of the heavy metal scavenger solution is 10-50 g/L;
the alginate accounts for 40-60% of the magnetic microspheres by mass;
the mass ratio of the heavy metal capture agent to the magnetic microspheres is 15-25%;
said Fe3O45-10% of the magnetic microspheres by mass;
the continuous mixing mode comprises stirring mixing and ultrasonic mixing;
the stirring and mixing time is 0.5-1 h;
the ultrasonic mixing time is 0.5-2 h.
Preferably, the pipe diameter of a capillary used in the liquid drop method is 0.5-2.0 mm;
the calcium source comprises calcium chloride;
the temperature of the low-temperature calcium source solution is-10 to-20 ℃;
the mass concentration of the low-temperature calcium source solution is 10-25%.
Preferably, the time for crosslinking and curing is 5-20 min;
the stirring speed of the crosslinking curing is 250-300 rpm;
the time for freezing polymerization is 36-48 h;
the temperature of the freezing polymerization is-40 to-12 ℃;
the freeze polymerization may further comprise one or more of thawing, separating, and washing steps.
The invention also provides application of the magnetic microsphere containing the heavy metal capture agent prepared by the preparation method in any one of the technical schemes or the magnetic microsphere containing the heavy metal capture agent prepared by the preparation method in any one of the technical schemes in the field of water treatment.
The invention provides a magnetic microsphere containing a heavy metal trapping agent, which is obtained by complexing and crosslinking alginate and calcium ions; the magnetic microspheres have a polymer network structure formed after complexing and crosslinking; the magnetic microspheres comprise heavy metal capture agent and Fe3O4. Compared with the prior art, the invention provides the magnetic microsphere containing the heavy metal capture agent and having the specific structure, the alginate with good biocompatibility is adopted to embed and fix the heavy metal capture agent and the magnetic particles, the magnetic microsphere has the specific internal network structure, the heavy metal capture agent is embedded and fixed in the alginate, the residue of the heavy metal capture agent in a water body is avoided, and therefore, the secondary pollution to the water body is basically avoided, the problems of biochemical inhibition and the like caused by the residue of the heavy metal capture agent are solved, the recycling of the heavy metal is synchronously realized, and the magnetic microsphere has good environmental and economic benefits; and Fe is embedded and fixed in the magnetic microspheres3O4The magnetic particles have magnetism, improve the adsorption performance and solid-liquid separation efficiency of heavy metals, and are beneficial to the application of the magnetic particles in the field of sewage treatment. In addition, the magnetic microsphere provided by the invention has developed internal pores, large actual effective specific surface area and high mechanical strength.
The magnetic microsphere containing the heavy metal capture agent provided by the invention mainly has two functions of adsorbing heavy metals, realizing solid-liquid separation and recycling heavy metals when being subsequently applied to treating heavy metal wastewater, and firstly, the magnetic microsphere is used for adsorbing heavy metals and realizing the solid-liquid separation function:
the magnetic microspheres have the same functions as the heavy metal capture agent, and meanwhile, the magnetic microspheres can be used for rapidly adsorbing the heavy metal in the wastewater, so that the capture efficiency of the heavy metal capture agent in the microspheres is improved, and the microspheres after saturated adsorption can be used for rapidly realizing solid-liquid separation under the action of an external magnetic field.
Secondly, the heavy metal recycling function:
taking the application of more sulfur-containing heavy metal capture agents as an example, the high-concentration hydroxyl in the alkaline solution can release heavy metals which are combined by coordination bonds through lone pair electrons provided by sulfur atoms in the microspheres again, so that the heavy metals adsorbed by the magnetic microspheres are eluted under alkaline conditions, and the purpose of recycling the heavy metals is achieved.
The magnetic microspheres provided by the invention have the characteristics of good treatment effect, wide raw material source, low cost, low toxicity, high degradability and the like, and have the property of recycling heavy metal resources, so that the standard treatment and heavy metal resource recycling of heavy metal wastewater are realized. The invention also provides a preparation process of the magnetic microsphere, the production process is simple and convenient, the control is easy, the cost of the alginate raw material is low, the environment is protected, the particle size of the microsphere is controllable, the magnetic microspheres with different sizes can be prepared according to different pipe diameters of the used microtubes, and the industrial scale production and application are more favorably realized.
Experimental results show that when the magnetic microspheres of the heavy metal trapping agent prepared by the invention are put into wastewater containing heavy metals, the treatment effect on the heavy metals is stable, most heavy metal ions can be chelated and precipitated, the removal rate can reach more than 99%, the adsorption efficiency is accelerated due to the magnetism of the microspheres, the treatment time can be shortened by 20% -40%, the treatment effect is superior to that of the traditional treatment process of the heavy metal trapping agent, the treatment of the heavy metal wastewater in industry is facilitated, and the secondary pollution to the environment is less.
Drawings
FIG. 1 is a schematic structural diagram of a magnetic microsphere containing a heavy metal scavenger according to the present invention;
FIG. 2 is a SEM scanning electron micrograph of the whole and part of the magnetic microsphere prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts the purity requirement which is conventional in the preparation field of industrial pure or metal wastewater treatment materials.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides a magnetic microsphere containing a heavy metal trapping agent, which is obtained by complexing and crosslinking alginate and calcium ions.
The magnetic microspheres have a polymer network structure formed after complexing and crosslinking.
The magnetic microspheres comprise heavy metal capture agent and Fe3O4。
In the present invention, the interior of the magnetic microsphere is preferably a network structure having pores.
In the present invention, the heavy metal scavenger is preferably embedded in the polymeric network structure.
In the present invention, the heavy metal scavenger preferably includes one or more of an organic nitrogen-containing heavy metal scavenger, an organic sulfur-containing heavy metal scavenger, and a natural modified polymer heavy metal scavenger, and more preferably an organic nitrogen-containing heavy metal scavenger, an organic sulfur-containing heavy metal scavenger, or a natural modified polymer heavy metal scavenger. Specifically, the organic nitrogen-based or organic sulfur-based compound preferably includes one or more of a heavy metal scavenger TMT-15, a heavy metal scavenger TMT102, a heavy metal scavenger DTC, a heavy metal scavenger DTCT, a heavy metal scavenger DTCR, and the like. The natural modified macromolecule heavy metal trapping agent preferably comprises a modified cellulose heavy metal trapping agent and/or a modified chitosan heavy metal trapping agent and the like.
In the present invention, the mass ratio of the heavy metal scavenger to the magnetic microspheres is preferably 15% to 25%, more preferably 17% to 23%, and still more preferably 19% to 21%.
In the present invention, the Fe3O4Preferably comprising Fe3O4And (3) nanoparticles.
In the present invention, the Fe3O4The nanoparticles are preferably embedded in the polymeric network structure.
In the present invention, the heavy metal scavenger is preferably complexed with the Fe3O4On the nanoparticles.
In the invention, the interior of the magnetic microsphere is of a net structure, the heavy metal trapping agent and Fe3O4The nanoparticles are all embedded in the polymeric network. Moreover, polyelectrolyte complexation reaction can occur between the heavy metal catcher and the alginate, so that a heavy metal catcher-alginate polyelectrolyte complex is formed, and the binding force between the heavy metal catcher and the alginate is increased. In addition, heavy metal scavenger and Fe3O4Nanoparticles, Fe3O4The nano particles and the alginate are compounded through physical action.
In the present invention, in the case of the present invention,said Fe3O4The particle size of the nanoparticles is preferably 10-40 nm, more preferably 15-35 nm, and more preferably 20-30 nm.
In the present invention, the Fe3O4The mass percentage of the magnetic microspheres is preferably 5-10%, more preferably 6-9%, and more preferably 7-8%.
In the invention, the alginate accounts for 40-60% of the magnetic microspheres by mass, preferably 44-56% of the magnetic microspheres by mass, and preferably 48-52% of the magnetic microspheres by mass.
In the invention, the particle size of the magnetic microsphere is preferably 1000-4000 μm, more preferably 1500-3500 μm, and more preferably 2000-3000 μm.
In the present invention, the magnetic microspheres preferably have a porous structure.
In the invention, the aperture of the magnetic microsphere is preferably 10-100 μm, more preferably 30-80 μm, and more preferably 50-60 μm.
In the present invention, the porosity of the magnetic microsphere is preferably 80% to 96%, more preferably 83% to 93%, and more preferably 86% to 90%.
In the invention, the specific surface area of the magnetic microspheres is preferably 60-90 m2(iv)/g, more preferably 65 to 85m2A more preferable range is 70 to 80 m/g2/g。
In the present invention, the magnetic microspheres are preferably magnetic microspheres embedded with a heavy metal capture agent.
In the invention, the magnetic microspheres are preferably magnetic microspheres for adsorbing heavy metals in wastewater.
In the present invention, the magnetic microspheres are preferably magnetic microspheres having a function of rapidly separating from wastewater.
The steps of the invention provide a magnetic microsphere containing a heavy metal trapping agent, the microsphere is approximately spherical in appearance, and the interior of the microsphere is of a mesh structure with super-large pores. The heavy metal trapping agent and the magnetic nano-particle Fe3O4Alginate and the like through a dynamic process of coupling of heat, mass transfer and polymerization reaction to form an oversized product with the particle size of 10-100 nmThe magnetic microsphere with a pore network structure has the advantages of high porosity of 95%, developed internal pores and good mass transfer effect. And heavy metal trapping agent and magnetic nano-particle Fe3O4Embedded in alginate, and the alginate is cross-linked, solidified and formed in calcium chloride solution. The alginate is a natural polyuronic acid, free carboxyl on a molecular chain of the natural polyuronic acid and free amino on a molecular chain of the heavy metal trapping agent generate polyelectrolyte complexation under the action of electrostatic force, so that the binding force of the natural polyuronic acid and the free carboxyl is enhanced, and the natural polyuronic acid is beneficial to recycling for many times. The magnetic microsphere can be combined with various heavy metal ions through adsorption, and simultaneously, the loaded magnetic nano-particle Fe in the magnetic microsphere is utilized3O4Can quickly adsorb heavy metals in the wastewater, is beneficial to improving the adsorption efficiency, and the adsorption effect can be the result of the combined action of ion exchange, chelation and surface complexation.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a magnetic microsphere containing a heavy metal capture agent according to the present invention.
The invention provides a preparation method of a magnetic microsphere containing a heavy metal trapping agent, which comprises the following steps:
1) mixing the heavy metal catching agent solution and the alginate solution, adding ferroferric oxide, and continuously mixing to obtain a mixed solution;
2) and (3) dropping the mixed solution obtained in the step into a low-temperature calcium source solution by adopting a liquid drop method, and obtaining the magnetic microspheres after crosslinking and solidification and then freeze polymerization.
The method comprises the steps of firstly mixing a heavy metal capture agent solution and an alginate solution, then adding ferroferric oxide, and continuously mixing to obtain a mixed solution.
In the invention, the concentration of the heavy metal scavenger solution is preferably 10-50 g/L, more preferably 15-45 g/L, more preferably 20-40 g/L, and more preferably 25-35 g/L.
In the invention, the alginate accounts for 40-60% of the magnetic microspheres by mass, preferably 44-56% of the magnetic microspheres by mass, and preferably 48-52% of the magnetic microspheres by mass.
In the present invention, the mass ratio of the heavy metal scavenger to the magnetic microspheres is preferably 15% to 25%, more preferably 17% to 23%, and still more preferably 19% to 21%.
In the present invention, the Fe3O4The mass percentage of the magnetic microspheres is preferably 5-10%, more preferably 6-9%, and more preferably 7-8%.
In the present invention, the means for continuing the mixing preferably includes agitation mixing and ultrasonic mixing.
In the invention, the stirring and mixing time is preferably 0.5-1 h, more preferably 0.6-0.9 h, and more preferably 0.7-0.8 h.
In the invention, the time of ultrasonic mixing is preferably 0.5-2 h, more preferably 0.8-1.7 h, and more preferably 1.1-1.4 h.
The invention further adopts a liquid drop method, the mixed solution obtained in the step is dropped into the low-temperature calcium source solution, and after crosslinking and solidification, the magnetic microspheres are obtained after freezing and polymerization.
In the invention, the tube diameter of the capillary tube adopted by the liquid drop method is preferably 0.5-2.0 mm, more preferably 0.8-1.7 mm, and more preferably 1.1-1.4 mm.
In the present invention, the calcium source preferably comprises calcium chloride. Specifically, the calcium chloride is a calcium chloride solution, and the concentration of the calcium chloride solution is preferably 20-70 mg/mL, more preferably 30-60 mg/mL, and more preferably 40-50 mg/mL.
In the present invention, the temperature of the low-temperature calcium source solution is preferably-10 to-20 ℃, more preferably-12 to-18 ℃, and more preferably-14 to-16 ℃.
In the present invention, the mass concentration of the low-temperature calcium source solution is preferably 10% to 25%, more preferably 13% to 22%, and still more preferably 16% to 18%.
In the invention, the time for crosslinking and curing is preferably 5-20 min, more preferably 8-17 min, and more preferably 11-14 min.
In the invention, the stirring speed of the crosslinking curing is preferably 250-300 rpm, more preferably 260-290 rpm, and more preferably 270-280 rpm. The invention adopts a specific stirring speed, so that the invention can keep forming microspheres with regular shapes.
In the invention, the time for the freeze polymerization is preferably 36 to 48 hours, more preferably 38 to 46 hours, and more preferably 40 to 44 hours.
In the present invention, the temperature of the freeze polymerization is preferably-40 to-12 ℃, more preferably-35 to-17 ℃, and still more preferably-30 to 22 ℃.
In the present invention, the freeze polymerization preferably includes one or more of thawing, separation and washing steps, more preferably, multiple of thawing, separation or washing.
The invention is a complete and refined integral preparation process, better ensures the structure, the appearance, the parameters and the performance of the embedded heavy metal catching agent magnetic microsphere, and further improves the adsorption performance, the separation performance and the recycling performance of the subsequent application, and the preparation method of the magnetic microsphere provided by the steps preferably comprises the following steps:
(1) preparing a heavy metal capture agent solution: weighing the solid or liquid of the heavy metal capture agent to be embedded, dispersing and dissolving the solid or liquid in water under the stirring condition, centrifuging the solution for 15-30 min, centrifuging and discarding the precipitate to prepare the solution (10-50 g/L, w/v) of the heavy metal capture agent.
(2) Preparing alginate mixed solution: weighing alginate (the alginate is one of sodium alginate or magnesium alginate), wherein the mass percentage of the alginate in the magnetic microspheres is 40-60%. Slowly dispersing and dissolving in water under mechanical stirring, slowly dripping heavy metal trapping agent solution after complete dissolution, wherein the mass percentage of the heavy metal trapping agent in the magnetic microspheres is 15-25%. Dispersing heavy metal catcher solution in alginate solution, and then dispersing magnetic Fe3O4Uniformly dispersing in alginate solution, continuously stirring and mixing for 0.5-1 h, and then performing ultrasonic treatment for 0.5-2 h to obtain the solution containing heavy metal capture agent and magnetic Fe3O4The mixed solution of (4) is stored for later use.
(3) Preparing magnetic microsphere with microtube by liquid drop method, pumping the mixed solution of heavy metal scavenger into microtube at constant flow rate to form at the end of microtubeDropping the heavy metal trapping agent mixed liquid drop into 10-25% calcium chloride solution at the low temperature of-10 to-20 ℃ under the action of gravity, quickly freezing to form balls, performing crosslinking solidification, stirring at a constant speed to avoid formed microsphere agglomeration, flushing residual calcium chloride solution on the surface by using water after the reaction is finished, quickly transferring to the condition of about-20 ℃ for freezing polymerization, performing polymerization reaction for 36-48 hours, thawing at normal temperature, separating the prepared microspheres by using a magnet, removing substances which cannot be attracted by the magnet, leaving magnetic microspheres, and cleaning the surfaces of the microspheres for several times by using a large amount of water to obtain alginate-embedded heavy metal trapping agent microspheres, wherein the magnetic Fe is embedded in the microspheres3O4Thus being beneficial to the adsorption and separation of heavy metals.
The invention can prepare magnetic microspheres with different particle sizes according to different pipe diameters of the used microtubes. Separating the prepared microspheres by using a magnet, removing substances which cannot be attracted by the magnet, leaving the microspheres with magnetism, washing the microspheres for a plurality of times by using deionized water, and storing the microspheres for later use.
The invention provides application of the magnetic microsphere containing the heavy metal capture agent prepared by any one of the technical schemes or the magnetic microsphere containing the heavy metal capture agent prepared by the preparation method of any one of the technical schemes in the field of water treatment.
The invention provides a magnetic microsphere embedded with a heavy metal capture agent, and a preparation method and application thereof. According to the invention, the alginate with good biocompatibility is used for embedding and fixing the heavy metal capture agent and the magnetic particles, and the alginate has a specific internal network structure, so that the heavy metal capture agent is embedded and fixed in the alginate, the heavy metal capture agent is prevented from remaining in a water body, and secondary pollution is not generated to the water body basically, thus the problems of biochemical inhibition and the like caused by the residue of the heavy metal capture agent are solved, the heavy metal resource recovery is synchronously realized, and the alginate has good environmental and economic benefits; and Fe is embedded and fixed in the magnetic microspheres3O4The magnetic particles have magnetism, improve the adsorption performance and solid-liquid separation efficiency of heavy metals, and are beneficial to the field of sewage treatment, in particular to electroplatingApplication in water treatment. In addition, the magnetic microsphere provided by the invention has developed internal pores, large actual effective specific surface area and high mechanical strength.
The magnetic microsphere containing the heavy metal capture agent provided by the invention mainly has two functions of adsorbing heavy metals, realizing solid-liquid separation and recycling heavy metals when being subsequently applied to treating heavy metal wastewater, and firstly, the magnetic microsphere is used for adsorbing heavy metals and realizing the solid-liquid separation function:
the magnetic microspheres have the same functions as the heavy metal capture agent, and meanwhile, the magnetic microspheres can be used for rapidly adsorbing the heavy metal in the wastewater, so that the capture efficiency of the heavy metal capture agent in the microspheres is improved, and the microspheres after saturated adsorption can be used for rapidly realizing solid-liquid separation under the action of an external magnetic field.
Secondly, the heavy metal recycling function:
taking the application of more sulfur-containing heavy metal capture agents as an example, the high-concentration hydroxyl in the alkaline solution can release heavy metals which are combined by coordination bonds through lone pair electrons provided by sulfur atoms in the microspheres again, so that the heavy metals adsorbed by the magnetic microspheres are eluted under alkaline conditions, and the purpose of recycling the heavy metals is achieved.
The magnetic microspheres provided by the invention have the characteristics of good treatment effect, wide raw material source, low cost, low toxicity, high degradability and the like, and have the property of recycling heavy metal resources, so that the standard treatment and heavy metal resource recycling of heavy metal wastewater are realized. The invention also provides a preparation process of the magnetic microsphere, the production process is simple and convenient, the control is easy, the cost of the alginate raw material is low, the environment is protected, the particle size of the microsphere is controllable, the magnetic microspheres with different sizes can be prepared according to different pipe diameters of the used microtubes, and the industrial scale production and application are more favorably realized.
Experimental results show that when the magnetic microspheres of the heavy metal trapping agent prepared by the invention are put into wastewater containing heavy metals, the treatment effect on the heavy metals is stable, most heavy metal ions can be chelated and precipitated, the removal rate can reach more than 99%, the adsorption efficiency is accelerated due to the magnetism of the microspheres, the treatment time can be shortened by 20% -40%, the treatment effect is superior to that of the traditional treatment process of the heavy metal trapping agent, the treatment of the heavy metal wastewater in industry is facilitated, and the secondary pollution to the environment is less.
For further illustration of the present invention, the following will describe in detail a magnetic microsphere containing a heavy metal scavenger and its preparation method and application in conjunction with the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
30.0g of heavy metal trapping agent solid is accurately weighed, dispersed and dissolved in 1L of water under the stirring condition, the solution is centrifuged for 20min, and the precipitate is centrifuged to prepare the required heavy metal trapping agent solution (10g/L, w/v). Accurately weighing 8.6g of sodium alginate, slowly dispersing and dissolving in 800mL of water under mechanical stirring, slowly dropwise adding a heavy metal capture agent solution after complete dissolution, dispersing the heavy metal capture agent solution in an alginate solution, and accurately weighing 4.0g of Fe3O4Powder and magnetic Fe3O4Uniformly dispersing in alginate solution, continuously stirring and mixing for 1h, and performing ultrasonic treatment for 1h to obtain the product containing heavy metal capture agent and magnetic Fe3O4The mixed solution of (4) is stored for later use.
Preparing magnetic microsphere with 0.5mm inner diameter microtube, and mixing the heavy metal scavenger at constant value of 10mm s-1Pumping the mixture into a microtube at an inlet flow rate, dropping the heavy metal scavenger mixture drop formed at the tail end of the microtube into a low-temperature 20% calcium chloride solution at-20 ℃ under the action of gravity, quickly freezing the mixture into balls, performing crosslinking solidification, stirring at a constant speed of 250rpm to avoid formed microsphere agglomeration, washing off the calcium chloride solution remaining on the surface after the reaction is finished, quickly transferring the calcium chloride solution to the condition of about-20 ℃ for freezing polymerization, performing normal-temperature thawing after the polymerization reaction is carried out for 48 hours, separating the prepared microspheres by using a magnet, and removing the microspheres which cannot be magnetically adsorbedKeeping magnetic microspheres from the substance attracted by iron, washing the surfaces of the microspheres for several times by using a large amount of water to obtain alginate-embedded heavy metal capture agent microspheres, wherein the microspheres are embedded with magnetic Fe3O4Thus being beneficial to the adsorption and separation of heavy metals.
The magnetic microspheres containing the heavy metal capture agent prepared in example 1 of the present invention were characterized.
Referring to fig. 2, fig. 2 is a SEM scanning electron micrograph of the whole and part of the magnetic microsphere prepared in example 1 of the present invention.
The magnetic microspheres containing the heavy metal capture agent prepared in example 1 of the present invention were subjected to a performance test.
Taking 500mL of certain chemical nickel electroplating wastewater, detecting the initial nickel content of a water sample to be 15mg/L, adding 0.36g of the embedded heavy metal capture agent magnetic microspheres, stirring for 20 minutes at the normal temperature of 300rpm, filtering, detecting the nickel content of water to be 0.076mg/L, and then removing the nickel with the removal rate of 99.5%. The magnetic microspheres are collected in a centralized manner, soaked and cleaned in 1mol/L NaOH solution, and heavy metals adsorbed by the magnetic microspheres are eluted under an alkaline condition, so that the aim of recycling the heavy metals is fulfilled, and the magnetic microspheres can be recycled.
Taking 500mL of countercurrent washing water after electro-plating coarsening and chrome plating, uniformly mixing in a beaker, and detecting initial Cr of a water sample3+The content is 50mg/L, 0.88g of the embedded heavy metal catching agent magnetic microspheres are added, the mixture is stirred for about 20 minutes under the normal temperature condition that the rotating speed is 300rpm, and the Cr of the effluent is filtered and detected3+The content is 0.127mg/L, in this case, for Cr3+The removal rate of the catalyst can reach 99.7 percent. The magnetic microspheres are collected in a centralized manner, soaked and cleaned in 1mol/L NaOH solution, and heavy metals adsorbed by the magnetic microspheres are eluted under an alkaline condition, so that the aim of recycling the heavy metals is fulfilled, and the magnetic microspheres can be recycled.
Taking 500mL of certain electroplating wastewater, uniformly mixing the wastewater in a beaker, and detecting initial Cr of a water sample3+The content of 25mg/L, the zinc content of 52mg/L and the nickel content of 30mg/L, 0.75g of the magnetic microspheres of the embedded heavy metal catching agent is added, and the mixture is stirred for 30 minutes at the normal temperature of 300rpmLeft and right, filtering and detecting the Cr in the effluent3+The content of the zinc is 0.206mg/L, the content of the zinc is 0.538mg/L, the content of the nickel is 0.214mg/L, and then the Cr is treated3+The removal rate of zinc and nickel can reach more than 99 percent. The magnetic microspheres are collected in a centralized manner, soaked and cleaned in 1mol/L NaOH solution, and heavy metals adsorbed by the magnetic microspheres are eluted under an alkaline condition, so that the aim of recycling the heavy metals is fulfilled, and the magnetic microspheres can be recycled.
Example 2
Weighing 20.0g of heavy metal scavenger solid, dispersing and dissolving in 1L of water under stirring, centrifuging the solution for 20min, centrifuging, and discarding the precipitate to obtain the required heavy metal scavenger solution (10g/L, w/v). Weighing 7.8g of sodium alginate, slowly dispersing and dissolving in 800mL of water under mechanical stirring, slowly dropwise adding a heavy metal capture agent solution after complete dissolution, dispersing the heavy metal capture agent solution in an alginate solution, and weighing 6.0g of Fe3O4Powder and magnetic Fe3O4Uniformly dispersing in alginate solution, continuously stirring and mixing for 1h, and performing ultrasonic treatment for 1h to obtain the product containing heavy metal capture agent and magnetic Fe3O4The mixed solution of (4) is stored for later use.
Preparing magnetic microsphere with 1.0mm inner diameter microtube, and mixing the heavy metal scavenger at constant value of 10mm s-1Pumping the mixture into a microtube at an inlet flow rate, dropping the heavy metal capture agent mixed liquid drop formed at the tail end of the microtube into 22% calcium chloride solution at the low temperature of-15 ℃ under the action of gravity, quickly freezing to form balls, performing crosslinking solidification, stirring at a constant speed of 270rpm to avoid formed microsphere agglomeration, flushing residual calcium chloride solution on the surface after the reaction is finished, quickly transferring the calcium chloride solution to the condition of about-25 ℃ for freezing polymerization, thawing at normal temperature after 40h of polymerization reaction, separating the prepared microspheres by using a magnet, removing substances which cannot be attracted by the magnet, leaving magnetic microspheres, and washing the surfaces of the microspheres for a plurality of times by using a large amount of water to obtain alginate-embedded heavy metal capture agent microspheres, wherein the magnetic Fe is embedded in the microspheres3O4Thus being beneficial to the adsorption and separation of heavy metals.
The magnetic microspheres containing the heavy metal capture agent prepared in example 2 of the present invention were subjected to a performance test.
Taking 500mL of certain chemical nickel electroplating wastewater, detecting the initial nickel content of a water sample to be 15mg/L, adding 0.40g of the embedded heavy metal capture agent magnetic microspheres, stirring for 20 minutes at the normal temperature of 300rpm, filtering to detect the nickel content of water to be 0.079mg/L, and then the removal rate of nickel can reach 99.5%. The magnetic microspheres are collected in a centralized manner, soaked and cleaned in 1mol/L NaOH solution, and heavy metals adsorbed by the magnetic microspheres are eluted under an alkaline condition, so that the aim of recycling the heavy metals is fulfilled, and the magnetic microspheres can be recycled.
Taking 500mL of countercurrent washing water after electro-plating coarsening and chrome plating, uniformly mixing in a beaker, and detecting initial Cr of a water sample3+The content is 50mg/L, 1.35g of the embedded heavy metal capture agent magnetic microspheres are added, the mixture is stirred for about 20 minutes at the normal temperature of 300rpm, and the Cr of the effluent is filtered and detected3+The content is 0.143mg/L, in this case for Cr3+The removal rate of the catalyst can reach 99.7 percent. The magnetic microspheres are collected in a centralized manner, soaked and cleaned in 1mol/L NaOH solution, and heavy metals adsorbed by the magnetic microspheres are eluted under an alkaline condition, so that the aim of recycling the heavy metals is fulfilled, and the magnetic microspheres can be recycled.
Taking 500mL of certain electroplating wastewater, uniformly mixing the wastewater in a beaker, and detecting initial Cr of a water sample3+The content of 25mg/L, the zinc content of 52mg/L and the nickel content of 30mg/L, 1.25g of the magnetic microspheres of the embedded heavy metal catching agent are added, the mixture is stirred for about 30 minutes at the normal temperature of 300rpm, and the Cr in the effluent is filtered and detected3+The content of the zinc is 0.236mg/L, the content of the zinc in the effluent is 0.519mg/L, the content of the nickel in the effluent is 0.220mg/L, and then the Cr is treated3+The removal rate of zinc and nickel can reach more than 99 percent. The magnetic microspheres are collected in a centralized manner, soaked and cleaned in 1mol/L NaOH solution, and heavy metals adsorbed by the magnetic microspheres are eluted under an alkaline condition, so that the aim of recycling the heavy metals is fulfilled, and the magnetic microspheres can be recycled.
Example 3
Weighing 40.0g of heavy metal scavenger solid inDispersing and dissolving in 1L water under stirring, centrifuging for 20min, centrifuging to remove precipitate, and making into the desired heavy metal scavenger solution (10g/L, w/v). Weighing 10.0g of sodium alginate, slowly dispersing and dissolving in 800mL of water under mechanical stirring, slowly dropwise adding a heavy metal capture agent solution after complete dissolution, dispersing the heavy metal capture agent solution in an alginate solution, and weighing 4.5g of Fe3O4Powder and magnetic Fe3O4Uniformly dispersing in alginate solution, continuously stirring and mixing for 1h, and performing ultrasonic treatment for 1h to obtain the product containing heavy metal capture agent and magnetic Fe3O4The mixed solution of (4) is stored for later use.
Preparing magnetic microsphere with 1.5mm inner diameter microtube, and mixing the heavy metal scavenger at constant value of 10mm s-1Pumping the mixture into a microtube at an inlet flow rate, dropping the heavy metal capture agent mixed liquid drop formed at the tail end of the microtube into 22% calcium chloride solution at the low temperature of-15 ℃ under the action of gravity, quickly freezing to form balls, performing crosslinking solidification, stirring at a constant speed of 270rpm to avoid formed microsphere agglomeration, flushing residual calcium chloride solution on the surface after the reaction is finished, quickly transferring the calcium chloride solution to the condition of about-25 ℃ for freezing polymerization, thawing at normal temperature after 40h of polymerization reaction, separating the prepared microspheres by using a magnet, removing substances which cannot be attracted by the magnet, leaving magnetic microspheres, and washing the surfaces of the microspheres for a plurality of times by using a large amount of water to obtain alginate-embedded heavy metal capture agent microspheres, wherein the magnetic Fe is embedded in the microspheres3O4Thus being beneficial to the adsorption and separation of heavy metals.
The magnetic microspheres containing the heavy metal capture agent prepared in example 3 of the present invention were subjected to a performance test.
Taking 500mL of certain chemical nickel electroplating wastewater, detecting the initial nickel content of a water sample to be 15mg/L, adding 0.20g of the embedded heavy metal capture agent magnetic microspheres, stirring for 20 minutes at the normal temperature of 300rpm, filtering to detect the nickel content of water to be 0.056mg/L, and then the removal rate of nickel can reach 99.6%. The magnetic microspheres are collected in a centralized manner, soaked and cleaned in 1mol/L NaOH solution, and heavy metals adsorbed by the magnetic microspheres are eluted under an alkaline condition, so that the aim of recycling the heavy metals is fulfilled, and the magnetic microspheres can be recycled.
Taking 500mL of countercurrent washing water after electro-plating coarsening and chrome plating, uniformly mixing in a beaker, and detecting initial Cr of a water sample3+The content is 50mg/L, 0.65g of the embedded heavy metal catching agent magnetic microspheres are added, the mixture is stirred for about 20 minutes at the normal temperature of 300rpm, and the Cr of the effluent is filtered and detected3+The content is 0.136mg/L, in this case, for Cr3+The removal rate of the catalyst can reach 99.7 percent. The magnetic microspheres are collected in a centralized manner, soaked and cleaned in 1mol/L NaOH solution, and heavy metals adsorbed by the magnetic microspheres are eluted under an alkaline condition, so that the aim of recycling the heavy metals is fulfilled, and the magnetic microspheres can be recycled.
Taking 500mL of certain electroplating wastewater, uniformly mixing the wastewater in a beaker, and detecting initial Cr of a water sample3+The content of 25mg/L, the zinc content of 52mg/L and the nickel content of 30mg/L, 0.60g of the magnetic microspheres of the embedded heavy metal catching agent is added, the mixture is stirred for about 30 minutes at the normal temperature of 300rpm, and the Cr in the effluent is filtered and detected3+The content is 0.172mg/L, the effluent zinc content is 0.471mg/L, the effluent nickel content is 0.188mg/L, and then the Cr content is adjusted3+The removal rate of zinc and nickel can reach more than 99 percent. The magnetic microspheres are collected in a centralized manner, soaked and cleaned in 1mol/L NaOH solution, and heavy metals adsorbed by the magnetic microspheres are eluted under an alkaline condition, so that the aim of recycling the heavy metals is fulfilled, and the magnetic microspheres can be recycled.
The magnetic microspheres embedded with heavy metal capture agents and the preparation method and application thereof provided by the present invention are described in detail above, and the principle and the embodiment of the present invention are illustrated herein by using specific examples, which are only used to help understand the method and the core idea of the present invention, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any combined method. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The magnetic microsphere containing the heavy metal catching agent is characterized by being obtained by complexing and crosslinking alginate and calcium ions;
the magnetic microspheres have a polymer network structure formed after complexing and crosslinking;
the magnetic microspheres comprise heavy metal capture agent and Fe3O4。
2. The magnetic microsphere of claim 1, wherein the magnetic microsphere has a network structure with pores inside;
the heavy metal scavenger is embedded in the polymeric network structure;
said Fe3O4Including Fe3O4A nanoparticle;
said Fe3O4Nanoparticles are embedded in the polymeric network structure.
3. The magnetic microsphere of claim 1, wherein the heavy metal scavenger is complexed with the Fe3O4On the nanoparticles;
said Fe3O4The particle size of the nanoparticles is 10-40 nm.
The alginate accounts for 40-60% of the magnetic microspheres by mass;
the heavy metal trapping agent comprises one or more of organic nitrogen-containing heavy metal trapping agents, organic sulfur-containing heavy metal trapping agents and natural modified high-molecular heavy metal trapping agents;
the mass ratio of the heavy metal capture agent to the magnetic microspheres is 15-25%.
4. The magnetic microsphere of claim 1, wherein the Fe is3O45-10% of the magnetic microspheres by mass;
the magnetic microspheres are embedded with heavy metal capture agents;
the magnetic microspheres are used for adsorbing heavy metals in the wastewater;
the magnetic microspheres are magnetic microspheres with a function of quickly separating the magnetic microspheres from wastewater.
5. The magnetic microsphere of claim 1, wherein the particle size of the magnetic microsphere is 1000 to 4000 μm;
the magnetic microspheres have a porous structure;
the aperture of the magnetic microsphere is 10-100 mu m;
the porosity of the magnetic microspheres is 80-96%;
the specific surface area of the magnetic microspheres is 60-90 m2/g。
6. A preparation method of magnetic microspheres containing a heavy metal trapping agent is characterized by comprising the following steps:
1) mixing the heavy metal catching agent solution and the alginate solution, adding ferroferric oxide, and continuously mixing to obtain a mixed solution;
2) and (3) dropping the mixed solution obtained in the step into a low-temperature calcium source solution by adopting a liquid drop method, and obtaining the magnetic microspheres after crosslinking and solidification and then freeze polymerization.
7. The preparation method according to claim 6, wherein the concentration of the heavy metal scavenger solution is 10 to 50 g/L;
the alginate accounts for 40-60% of the magnetic microspheres by mass;
the mass ratio of the heavy metal capture agent to the magnetic microspheres is 15-25%;
said Fe3O45-10% of the magnetic microspheres by mass;
the continuous mixing mode comprises stirring mixing and ultrasonic mixing;
the stirring and mixing time is 0.5-1 h;
the ultrasonic mixing time is 0.5-2 h.
8. The preparation method according to claim 6, wherein the diameter of the capillary tube used in the liquid drop method is 0.5-2.0 mm;
the calcium source comprises calcium chloride;
the temperature of the low-temperature calcium source solution is-10 to-20 ℃;
the mass concentration of the low-temperature calcium source solution is 10-25%.
9. The preparation method according to claim 6, wherein the time for the crosslinking and curing is 5-20 min;
the stirring speed of the crosslinking curing is 250-300 rpm;
the time for freezing polymerization is 36-48 h;
the temperature of the freezing polymerization is-40 to-12 ℃;
the freeze polymerization may further comprise one or more of thawing, separating, and washing steps.
10. The application of the magnetic microsphere containing the heavy metal capture agent according to any one of claims 1 to 5 or the magnetic microsphere containing the heavy metal capture agent prepared by the preparation method according to any one of claims 6 to 9 in the field of water treatment.
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Application publication date: 20220412 |