CN113713630B - Composite membrane synthesis method for adsorbing gaseous mercury and composite membrane - Google Patents
Composite membrane synthesis method for adsorbing gaseous mercury and composite membrane Download PDFInfo
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Abstract
The application belongs to the technical field of air purification, and particularly relates to a method for synthesizing a composite membrane for adsorbing gaseous mercury and a composite membrane. The synthesis method comprises the following steps: preparing a multi-wall carbon nano tube solution, and preparing a proper amount of multi-wall carbon nano tubes into a uniform solution with a certain concentration through ultrasonic stirring treatment; preparing a film, and uniformly attaching the multi-wall carbon nano tube subjected to ultrasonic stirring on the surface of a non-woven fabric in a vacuum filtration mode; the film is immersed once, N-methyl pyrrolidone and pyrrole monomer are prepared into solution according to a certain volume ratio, and a proper amount of polyvinylidene fluoride powder is added, and after heating and stirring are carried out uniformly, the film is immersed; preparing an acidic ferric chloride aqueous solution containing sodium dodecyl benzene sulfonate, and re-immersing the film in the solution; washing and drying the film, washing the film which is dipped twice, and drying in vacuum to prepare the composite film.
Description
Technical Field
The application belongs to the technical field of air purification, and particularly relates to a method for synthesizing a composite membrane for adsorbing gaseous mercury and a composite membrane.
Background
In recent years, as environmental problems are increasingly severe, environmental laws and regulations are stricter and stricter on pollutant emission, and laws and regulations such as ' twelve five ' planning for controlling atmospheric pollution in key areas ' and ' emission standard of atmospheric pollutants in thermal power plants ' are also revised and issued in China later to control and treat mercury emission. In addition, as the environmental awareness of people is enhanced, the requirement on the quality of the ambient air is higher and higher, and people pay more attention to the environmental quality of rooms, work and the like. A large number of data researches and studies show that various pollutants in the air can cause serious harm to human health, and are the main reasons for increasing the incidence rate of respiratory diseases and cardiovascular and cerebrovascular diseases. The pollutant enters the human body through respiration, damages the respiratory system, the immune system and the blood system of the human body, and is highly likely to cause a series of diseases, especially heavy metals in the air, has strong toxicity, can carry out bioaccumulation, seriously affects the health of the human body, and even can affect the surrounding environment of the polluted serious area. Research shows that the air contains heavy metals including mercury accounting for total pollutantsThe proportion of the heavy metals is less than 1%, but most of the heavy metals are carcinogenic and toxic harmful substances, and cause immeasurable harm to human bodies and surrounding environments. Heavy metal Hg 0 The characteristics of long-distance migration, lasting existence and biological accumulation in the atmosphere are utilized, and the biological agent has serious harm to human health and environment.
Currently, research and application for removal of this contamination can be divided into: modified adsorption, heterogeneous catalytic oxidation and liquid phase oxidation, wherein the activated carbon adsorption method has been used for removing mercury from flue gas of a power plant, and other methods are mostly in experimental research stages. The traditional mercury removal mode is mainly realized by electric dust removal, wet flue gas desulfurization and denitration equipment, but the traditional mercury removal mode is not mainly used for mercury removal equipment, and the treatment effect is very limited. The active carbon spraying technology is mature at present and has an applied mode abroad, but the large-scale application of the technology is greatly limited by high operation cost, low active carbon utilization rate, difficult adsorbent regeneration and small adsorption quantity. In addition, there are various technologies for removing mercury by oxidation, but most of the technologies are aimed at removing mercury from flue gas, and the technologies are in a research and experimental stage, and have long routes away from practical application. And the methods are mainly applied to flue gas mercury removal, and air pollution in another place is easily ignored-an industrial production workshop, and the poor air condition threatens the health of workers at any time. Air purification for indoor/workshop is different from flue gas mercury removal, and needs mild environment, simple and compact process and efficient purification effect.
Disclosure of Invention
In order to reduce the pollution of heavy metal mercury in the air to a greater extent, particularly the pollution of elemental mercury comprising the indoor air of a metallurgical production workshop and a nearby residential area, the application aims to remove the heavy metal mercury through a membrane technology air purification system and recycle the heavy metal mercury, thereby providing a better air quality environment for people working and living in severe environments. The prior activated carbon mercury removal technology has complex equipment process, low activated carbon utilization rate and high equipment funds, and the application aims to improve the utilization rate of adsorption active substances in a membrane technology mode and reduce equipment requirements at the same time, thereby being capable of adapting to wider application range of workshop production/working life and other scenes.
In order to achieve the above purpose, the present application provides the following technical solutions:
a method for synthesizing a composite membrane for adsorbing gaseous mercury comprises the following steps:
preparing a multi-wall carbon nano tube solution, and preparing a proper amount of multi-wall carbon nano tubes into a uniform solution with a certain concentration through ultrasonic stirring treatment;
preparing a film, and uniformly attaching the multi-wall carbon nano tube subjected to ultrasonic stirring on the surface of a non-woven fabric in a vacuum filtration mode;
the film is immersed once, N-methyl pyrrolidone and pyrrole monomer are prepared into solution according to a certain volume ratio, and a proper amount of polyvinylidene fluoride powder is added, and after heating and stirring are carried out uniformly, the film is immersed;
preparing an acidic ferric chloride aqueous solution containing sodium dodecyl benzene sulfonate, and re-immersing the film in the solution;
washing and drying the film, washing the film which is dipped twice, and drying in vacuum to prepare the composite film.
Further, in the step of preparing the film, the multi-wall carbon nanotubes are uniformly attached to the surface of the non-woven fabric and then are kept stand for 1h at room temperature.
Further, in the primary film dipping step, preparing a solution, stirring for 2 hours at 60 ℃ to dissolve polyvinylidene fluoride and ensure that the solution is uniform; after standing, the film was immersed in the solution for 2 hours and then taken out.
Further, in the film secondary impregnation step, an acidic aqueous solution of ferric chloride is prepared as an acidic aqueous solution of ferric chloride containing 3g/L sodium dodecyl benzene sulfonate of 0.3 mol/L; the film was immersed in the solution and taken out after 2 hours.
Further, in the film washing and drying step, the secondarily immersed film is washed with secondary absolute ethyl alcohol and water, and then the film is dried in vacuum at 60 ℃ for 12 hours.
Further, the content of the multiwall carbon nanotubes in the step of preparing the film is 2.6-15.6 g/m2.
Further, the concentration of pyrrole monomer in one impregnation of the film is 0.3-2 mol/L, and the concentration of polyvinylidene fluoride is 2-12 g/L.
Further, the content of the multiwall carbon nanotube in the film preparation step is 7.8-10.4 g/m < 2 >; the concentration of pyrrole monomer is 0.8-1.5 mol/L and the concentration of polyvinylidene fluoride is 5-10 g/L in one-time dipping of the film.
A composite membrane for adsorbing gaseous mercury, and the composite membrane prepared by the steps.
The membrane synthesized by the application is used for carrying out mercury removal treatment on the mercury-containing gas, and can achieve higher treatment effect in short membrane passing time. The throughput was 15.6m when air was passed through the film at a flow rate of 1L/min 3 /(h·m 2 ) The removal efficiency of the elemental mercury in the air can reach 90-98 percent. The method is used in a typical metallurgical production workshop (0.04 mg/m) 3 ) Under the condition, the maximum allowable mercury concentration of 0.01mg/m in the air of the current production workshop can be met 3 Standard requirements. The method can greatly reduce heavy metal mercury pollution in the air, provides a good environment for people working and living in severe environments, and has high mercury treatment efficiency, high treatment rate, simple treatment process, no additional energy consumption, small occupied space, good environmental benefit and economic benefit and wide application prospect compared with the current countermeasures for workshop/indoor mercury pollution.
The beneficial effects of adopting above-mentioned technical scheme to produce lie in:
1) The method is novel, the removal of the elemental mercury is realized by adopting a membrane technology, the method has the characteristics of simple and compact process and high efficiency, and the method can achieve good purification effect under the conditions of daily life working environments of people such as indoor/workshops and the like.
2) The membrane of the application adopts non-woven fabrics as a support, polypyrrole-multiwall carbon nano tubes as active sites and R contained 2 The NH.HCl structure carries out mercury removal. The membrane structure has very small resistance to gas, can adapt to the condition of large gas velocity and flow, and realizes the rapid removal of gaseous mercury in space.
3) The film of the application has very large adsorption capacity which is about 30 times of the adsorption capacity of active carbon, the adsorption capacity can reach 5.76mg/g, and the film has the characteristic of high utilization rate.
4) The film can be reused, and can adsorb more Hg 0 After that, the original treatment efficiency can be recovered by only immersing in an acidic NaCl solution for a period of time.
Drawings
FIG. 1 shows Hg removal from a gas phase 0 Schematic of the experiment.
Wherein:
(a) Nitrogen gas
(b) Mercury vapor tube
(c) Flowmeter for measuring flow rate
(d) Gas mixing bottle
(e) Membrane reactor
(f) A mercury detector.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application discloses a method for synthesizing a composite membrane for adsorbing gaseous mercury. The preparation method comprises the following steps: 1) Uniformly attaching the multi-wall carbon nano tubes after ultrasonic treatment on the surface of the non-woven fabric in a vacuum filtration mode; 2) Preparing N-methyl pyrrolidone and pyrrole monomer into solution according to a certain volume ratio, adding a proper amount of adhesive polyvinylidene fluoride powder, heating and stirring uniformly, and immersing the film therein; 3) Preparing an acidic aqueous solution of ferric chloride containing a surfactant sodium dodecyl benzene sulfonate, and re-immersing the film in the solution; 4) And taking out the film, washing with absolute ethyl alcohol and water for multiple times, and then drying in vacuum to obtain the film. The film prepared by the method can adsorb gaseous mercury with high efficiency, has large adsorption capacity, and can be desorbed in a dipping mode for recycling.
The synthesis method of the application comprises the following steps: the synthesis method mainly adopts the methods of vacuum filtration, impregnation and phase inversion. The multi-wall carbon nano tube is attached to the non-woven fabric through vacuum filtration, but the adhesion effect is not good at the moment; then, dipping the polymer into an organic solution containing an adhesive and polypyrrole, dipping the polymer into an oxidant polymerization solution to enable the adhesive to complete phase inversion, and simultaneously polymerizing pyrrole monomers to complete further adhesion and adhesion of active substances; finally, washing and drying are carried out to obtain the film.
The mercury removal mechanism of the application is as follows:
the mercury removal mechanism mainly depends on the formation of pyrrole hydrochloride R on the synthesized film 2 The NH.HCl structure is used for adsorption mercury removal. The reaction mechanism is as follows:
Hg 0 (g)+R 2 NH·HCl→R 2 NH·HCl-Hg 0 (ad)
R 2 NH·HCl-Hg 0 (ad)→R 2 NH 2 -Cl-Hg
2R 2 NH 2 -Cl-Hg→R 2 NH 2 -Cl-Hg-Hg-Cl-H 2 NR 2
R 2 NH 2 -Cl-Hg+R 2 NH·HCl→R 2 NH 2 -Cl-Hg-Cl-H 2 NR 2
as a specific synthetic preparation example:
1) Preparing a proper amount of multiwall carbon nanotubes (MWCNTs) into a uniform solution with a certain concentration through ultrasonic stirring treatment;
2) Uniformly attaching multi-wall carbon nanotubes (MWCNTs) on the surface of the non-woven fabric in a vacuum filtration mode, and standing for 1h at room temperature;
3) Preparing N-methyl pyrrolidone (NMP) and pyrrole monomer (Py) into organic solution according to a certain volume ratio, adding a proper amount of adhesive polyvinylidene fluoride (PVDF) powder, stirring for 2h at 60 ℃ to dissolve the polyvinylidene fluoride (PVDF) and ensure that the solution is uniform,
4) Immersing the film after standing into the organic solution for 2 hours, and taking out;
5) Preparing 0.3mol/L ferric chloride acid aqueous solution containing 3g/L of surfactant Sodium Dodecyl Benzene Sulfonate (SDBS), soaking the film into the solution again to convert polyvinylidene fluoride (PVDF) phase, polymerizing pyrrole monomer (Py), and taking out about 2 hours;
6) And taking out the film, washing the film by absolute ethyl alcohol and water for a plurality of times, and then drying the film at 60 ℃ in vacuum for 12 hours to finish the preparation of the film.
Wherein the content of the multi-wall carbon nano tube is 2.6-15.6 g/m 2 Preferably 7.8 to 10.4g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of pyrrole monomer is 0.3-2 mol/L, preferably 0.8-1.5 mol/L, and the concentration of polyvinylidene fluoride is 2-12 g/L, preferably 5-10 g/L; the polymerization solution used was a 3g/L acidic aqueous solution of 0.3mol/L ferric chloride of Sodium Dodecyl Benzene Sulfonate (SDBS) as a surfactant.
The composite membrane for adsorbing gaseous mercury prepared by the present application comprises: a supporting material non-woven fabric, a polypyrrole-multiwall carbon nanotube composite film structure and a prepared oxidant polymerization solution. The membranes produced by this synthesis have a very excellent mercury removal effect.
The polypropylene nonwoven fabric plays a supporting role in order to enable the polypyrrole-multiwall carbon nanotube composite film to be attached thereto. The important reason for selecting the polypropylene non-woven fabric is that the porous air permeability is good, the weight is light and flexible, and the cost is low.
The polypyrrole-multi-wall carbon nano tube composite film structure is a main structure of the film, and the multi-wall carbon nano tube has a large number of pore structures, so that a great amount of polymerization bonding space can be provided for polypyrrole; polypyrrole is the main active substance, and the nitrogen-containing functional group on the polypyrrole is the main active site and combines with chloride ions to form a structure with adsorption activity on mercury.
The aqueous polymerization solution contains the following substances: ferric chloride, sodium Dodecyl Benzene Sulfonate (SDBS) and hydrochloric acid, wherein the oxidability of the ferric chloride can polymerize pyrrole monomers, the sodium dodecyl benzene sulfonate is used as a surfactant to enable the reaction to be more stable, more iron, chlorine and hydrogen ions are reserved, the hydrochloric acid is used for providing an acidic environment, so that the iron ions can have better oxidability, and meanwhile, the pH value change caused by the surfactant is regulated.
The membrane synthesized by the application is used for carrying out mercury removal treatment on the mercury-containing gas, and can achieve higher treatment effect in short membrane passing time. The throughput was 15.6m when air was passed through the film at a flow rate of 1L/min 3 /(h·m 2 ) The removal efficiency of the elemental mercury in the air can reach 90-98 percent. The method is used in a typical metallurgical production workshop (0.04 mg/m) 3 ) Under the condition, the maximum allowable mercury concentration of 0.01mg/m in the air of the current production workshop can be met 3 Standard requirements. The method can greatly reduce heavy metal mercury pollution in the air, provides a good environment for people working and living in severe environments, and has high mercury treatment efficiency, high treatment rate, simple treatment process, no additional energy consumption, small occupied space, good environmental benefit and economic benefit and wide application prospect compared with the current countermeasures for workshop/indoor mercury pollution.
The method is novel, the removal of the elemental mercury is realized by adopting a membrane technology, the method has the characteristics of simple and compact process and high efficiency, and the method can achieve good purification effect under the conditions of daily life working environments of people such as indoor/workshops and the like.
The membrane in the application adopts non-woven fabrics as a support, polypyrrole-multiwall carbon nanotubes as active sites, and the mercury is removed by a contained R2NH.HCl structure. The membrane structure has very small resistance to gas, can adapt to the condition of large gas velocity and flow, and realizes the rapid removal of gaseous mercury in space.
The film of the application has very large adsorption capacity which is about 30 times of the adsorption capacity of active carbon, the adsorption capacity can reach 5.76mg/g, and the film has the characteristic of high utilization rate.
The film can be reused, and after adsorbing more Hg0, the film can restore the original treatment efficiency by only immersing in an acidic NaCl solution for a period of time.
The following examples were carried out in mercury removal experiments:
example 1
Amount of active substance in Synthesis
Vacuum filtration of multiwall carbon nanotube amount: 0.04g
Concentration of impregnated pyrrole monomer: 1mol/L
The reaction conditions for purifying and removing mercury of air are shown in table 1
TABLE 1 reaction conditions
| Conditions (conditions) | Range |
| Air flow rate | 1L/min |
| Membrane area | 38.5cm 2 |
| Throughput of treatment | 15.6m 3 /(h·m 2 ) |
| Treatment temperature | Room temperature (20-25 ℃ C.) |
The air is subjected to mercury removal and purification treatment under the conditions, and the efficiency of 92% can be achieved.
Example 2
Amount of active substance in Synthesis
Vacuum filtration of multiwall carbon nanotube amount: 0.05g
Concentration of impregnated pyrrole monomer: 1mol/L
The reaction conditions for purifying and removing mercury of air are shown in Table 2
TABLE 2 reaction conditions
| Conditions (conditions) | Range |
| Air flow rate | 1L/min |
| Membrane area | 38.5cm 2 |
| Throughput of treatment | 15.6m 3 /(h·m 2 ) |
| Treatment temperature | Room temperature (20-25 ℃ C.) |
The air is subjected to mercury removal and purification treatment under the conditions, so that the efficiency of 98% can be achieved.
Example 3
Amount of active substance in Synthesis
Vacuum filtration of multiwall carbon nanotube amount: 0.04g
Concentration of impregnated pyrrole monomer: 2mol/L
The reaction conditions for purifying and removing mercury of air are shown in Table 3
TABLE 3 reaction conditions
| Conditions (conditions) | Range |
| Air-conditionerFlow rate | 1L/min |
| Membrane area | 38.5cm 2 |
| Throughput of treatment | 15.6m 3 /(h·m 2 ) |
| Treatment temperature | Room temperature (20-25 ℃ C.) |
The air is subjected to mercury removal and purification treatment under the conditions, so that the efficiency of 98% can be achieved.
Example 4
Amount of active substance in Synthesis
Vacuum filtration of multiwall carbon nanotube amount: 0.04g
Concentration of impregnated pyrrole monomer: 1mol/L
The reaction conditions for purifying and removing mercury of air are shown in Table 4
TABLE 4 reaction conditions
| Conditions (conditions) | Range |
| Air flow rate | 0.5L/min |
| Membrane area | 38.5cm 2 |
| Throughput of treatment | 7.8m 3 /(h·m 2 ) |
| Treatment temperature | Room temperature (20-25 ℃ C.) |
The air is subjected to mercury removal and purification treatment under the conditions, and the efficiency can reach 96%.
Example 5
Amount of active substance in Synthesis
Vacuum filtration of multiwall carbon nanotube amount: 0.04g
Concentration of impregnated pyrrole monomer: 1mol
The reaction conditions for purifying and removing mercury of air are shown in Table 5
TABLE 5 reaction conditions
| Conditions (conditions) | Range |
| Air flow rate | 2L/min |
| Membrane area | 38.5cm 2 |
| Throughput of treatment | 31.2m 3 /(h·m 2 ) |
| Treatment temperature | Room temperature (20-25 ℃ C.) |
The air is subjected to mercury removal and purification treatment under the conditions, so that the efficiency of 87% can be achieved.
It will be apparent to those skilled in the art that the foregoing has shown and described embodiments of the application with no difficulty in achieving the functional features described above, both in programming and technical computing implementation, and that numerous changes, modifications, substitutions and alterations may be made hereto without departing from the spirit and scope of the application as defined by the appended claims and their equivalents.
Claims (9)
1. The synthesis method of the composite membrane for adsorbing gaseous mercury is characterized by comprising the following steps:
preparing a multi-wall carbon nano tube solution, and preparing a proper amount of multi-wall carbon nano tubes into a uniform solution with a certain concentration through ultrasonic stirring treatment;
preparing a film, and uniformly attaching the multi-wall carbon nano tube subjected to ultrasonic stirring on the surface of a non-woven fabric in a vacuum filtration mode;
the film is immersed once, N-methyl pyrrolidone and pyrrole monomer are prepared into solution according to a certain volume ratio, and a proper amount of polyvinylidene fluoride powder is added, and after heating and stirring are carried out uniformly, the film is immersed;
preparing an acidic ferric chloride aqueous solution containing sodium dodecyl benzene sulfonate, and re-immersing the film in the solution;
washing and drying the film, washing the film which is dipped twice, and drying in vacuum to prepare the composite film.
2. The method for synthesizing a composite membrane for adsorbing gaseous mercury according to claim 1, wherein in the step of preparing the thin film, the multi-walled carbon nanotubes are uniformly attached to the surface of the nonwoven fabric and then allowed to stand at room temperature for 1 hour.
3. The method for synthesizing a composite membrane for adsorbing gaseous mercury according to claim 1, wherein in the step of immersing the membrane once, the prepared solution is stirred for 2 hours at 60 ℃ to dissolve polyvinylidene fluoride and ensure that the solution is uniform; after standing, the film was immersed in the solution for 2 hours and then taken out.
4. The method for synthesizing a composite membrane for adsorbing gaseous mercury according to claim 1, wherein in the step of secondarily immersing the membrane, an acidic aqueous solution of ferric chloride is prepared as an acidic aqueous solution of 0.3mol/L ferric chloride containing 3g/L sodium dodecyl benzene sulfonate; the film was immersed in the solution and taken out after 2 hours.
5. The method for synthesizing a composite membrane for adsorbing gaseous mercury according to claim 1, wherein in the step of washing and drying the membrane, the twice immersed membrane is washed with absolute ethanol and water a plurality of times, and the membrane is dried in vacuum at 60 ℃ for 12 hours.
6. The method for synthesizing a composite membrane for adsorbing gaseous mercury according to any one of claims 1 to 5, wherein the multi-walled carbon nanotube content in the step of preparing the thin film is 2.6 to 15.6g/m 2 。
7. The method for synthesizing a composite membrane for adsorbing gaseous mercury according to claim 6, wherein the concentration of pyrrole monomer in one impregnation of the membrane is 0.3-2 mol/L, and the concentration of polyvinylidene fluoride is 2-12 g/L.
8. The method for synthesizing a composite membrane for adsorbing gaseous mercury according to claim 7, wherein the multi-walled carbon nanotube content in the step of preparing the thin film is 7.8-10.4 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of pyrrole monomer is 0.8-1.5 mol/L and the concentration of polyvinylidene fluoride is 5-10 g/L in one-time dipping of the film.
9. A composite membrane for adsorbing gaseous mercury, characterized in that the composite membrane is prepared by the method according to any one of claims 1-8.
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| KR20110008518A (en) * | 2009-07-20 | 2011-01-27 | 주식회사 엑사이엔씨 | Method for manufacturing carbon nano tube solution having polymer and method for manufacturing transparency conductivity film using the same and transparency conductivity film manufacured by the method |
| CN108744989A (en) * | 2018-05-29 | 2018-11-06 | 华北电力大学（保定） | A kind of high throughput doped polypyrrole high polymer conductive ultrafiltration membrane preparation method |
| CN109052542A (en) * | 2018-09-06 | 2018-12-21 | 苏州佰锐生物科技有限公司 | A kind of preparation method for the modified carbon nano-tube removing mercury ions in waste water |
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