CN115554864B - Chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold element in water - Google Patents
Chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold element in water Download PDFInfo
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- CN115554864B CN115554864B CN202211415401.4A CN202211415401A CN115554864B CN 115554864 B CN115554864 B CN 115554864B CN 202211415401 A CN202211415401 A CN 202211415401A CN 115554864 B CN115554864 B CN 115554864B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold elements in a water body, and belongs to the technical field of fiber membrane preparation. The invention is used for solving the technical problems that the specific surface area of a chitosan-based fiber film is smaller, the adsorption capacity of the chitosan-based fiber film needs to be improved, the nanoparticle adsorbent is easy to agglomerate in the adsorption process and the separation and purification of gold ions recovered by adsorption are difficult when gold in wastewater is recovered by adsorption, and the invention comprises the following steps: weighing 20-30 parts of polyvinyl alcohol solution, 30-90 parts of chitosan solution and 1-2 parts of surfactant according to parts by weight, adding into a beaker, stirring, placing the beaker into a water bath environment with the temperature of 45-55 ℃, and stirring for 2-3 hours to obtain spinning solution. The invention not only effectively improves the specific surface area of the electrostatic spinning fiber membrane, but also reduces the adsorbed metal ions, effectively improves the recovery efficiency of noble metals, and reduces the recovery time and the technical cost of noble metals.
Description
Technical Field
The invention relates to the technical field of fiber membrane preparation, in particular to a chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold element in water.
Background
Gold is widely used in the monetary, jewelry and electrical industries due to its rarity, ductility and stability. The nano gold particles play an important role in drug delivery, photocatalysis, trace substance detection and the like. Since exploitation and refining of electronic waste and industrial wastewater can generate a large amount of gold-containing wastewater, gold in the wastewater is recycled, which is certainly a solution for alleviating gold ore consumption.
In the prior art, gold in wastewater is generally recovered by adopting an adsorption method, and the adsorption method has the advantages of simple operation, low cost, no secondary pollution and the like, and is recognized as one of the best methods for recovering gold from two main sources of gold-containing wastewater (electronic waste and wastewater discharged in gold exploitation and refining processes). In contrast, other processes such as solvent extraction, ion exchange, metal reduction, chemical deposition and electrolysis limit the reaction conditions to some extent and require additional heat sources or specially tailored expensive equipment and must face the risk of introducing byproducts.
In order to effectively recover gold by using an adsorption technology, a material with rich sulfur-containing and nitrogen-containing functional groups is required to be selected as a substrate material, chitosan (CS) is synthesized by deacetylation reaction of chitin, and each chain has two primary amino groups and one hydroxyl group, so that the chitosan is a good substrate material, however, the chitosan has strong solubility under an acidic condition, and the application of the chitosan in recovering gold from an actual solution is limited, and the prior art is modified by modifying the original chitosan, including physical composition and chemical composition. Although chitosan of different physical structure and chemical composition has been synthesized for adsorbing gold ions in water, there are still some disadvantages:
1) The chitosan-based materials (such as gel and beads) have oversized scale and relatively low surface area, but the chitosan nano materials are easy to agglomerate in the adsorption process;
2) Almost all forms of chitosan, whether in bead, granular or gel form, are difficult to separate after adsorbing gold ions from solution, but the addition of magnetic materials reduces recovery efficiency;
3) Current research is mainly focused on amino cross-linking, free hydroxyl groups are unchanged, and maximum adsorption capacity is limited.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold elements in a water body, which is used for solving the technical problems that when the chitosan-based fiber membrane is used for recovering gold in wastewater in the prior art, the specific surface area of the chitosan-based fiber membrane is smaller, the adsorption capacity of the chitosan-based fiber membrane needs to be improved, the agglomeration phenomenon of gold easily occurs in the adsorption process, the separation and purification of gold ions recovered by adsorption are difficult, and the recovery efficiency is low.
The aim of the invention can be achieved by the following technical scheme:
a chitosan-based electrostatic spinning fiber film capable of efficiently recovering gold element in water comprises the following operation steps:
s1, weighing 20-30 parts of polyvinyl alcohol solution, 30-90 parts of chitosan solution and 1-2 parts of surfactant according to parts by weight, adding into a beaker, stirring, placing the beaker in a water bath environment with the temperature of 45-55 ℃, and stirring for 2-3 hours to obtain spinning solution;
s2, adding spinning solution, and preparing an electrostatic spinning fiber membrane primary product through electrostatic spinning;
s3, cutting and cleaning the primary product of the electrostatic spinning film to obtain a crude product of the electrostatic spinning fiber film;
s4, placing the electrostatic spinning film crude product in a beaker, adding 10-20 parts by weight of 50wt% glutaraldehyde aqueous solution into the beaker, standing for 4-6 hours, pouring out the glutaraldehyde aqueous solution in the beaker, adding 10-20 parts by weight of modified solution into the beaker, placing the beaker on an oscillator for oscillating for 4-6 hours, and cleaning to obtain an electrostatic spinning fiber film finished product, wherein the modified solution is prepared by uniformly mixing 50-100 parts by weight of absolute ethyl alcohol, 25-50 parts by weight of 2.2wt% sulfuric acid solution, 25-50 parts by weight of 2.5wt% thiourea solution and 2-4 parts by weight of formaldehyde solution.
Further, the preparation method of the polyvinyl alcohol solution in the step S1 is as follows: 2-6 parts of polyvinyl alcohol and 20-60 parts of purified water are weighed according to parts by weight, the mixture is added into a beaker, the beaker is placed in a water bath environment with the temperature of 85-95 ℃, stirring is carried out for 10-14 hours, and the polyvinyl alcohol is dissolved, so that a polyvinyl alcohol solution is obtained.
Further, the preparation method of the chitosan solution in the step S1 is as follows: 1-3 parts of chitosan, 25-85 parts of glacial acetic acid and 3-9 parts of purified water are weighed according to parts by weight, the mixture is added into a beaker, the beaker is placed in a water bath environment with the temperature of 45-55 ℃, stirring is carried out for 6-10 hours, and chitosan is dissolved, so that a chitosan solution is obtained.
Further, the surfactant in the step S1 is composed of one or more of octyl phenyl polyoxyethylene ether, laurinol polyoxyethylene ether, secondary alcohol polyoxyethylene ether and octanol polyoxyethylene ether, and the deacetylation degree of chitosan is more than 99%.
Further, the electrostatic spinning in the step S2 includes the following operation steps:
a1, taking a stainless steel roller as a receiver, wrapping a layer of silicone paper outside the stainless steel roller, wherein the rotating speed of the stainless steel roller is 550-650 rpm;
a2, setting the spinning voltage to be 23.1kV, setting the distance between a spray head and a stainless steel roller to be 9-11 cm, setting the environment temperature to be 23-28 ℃ and setting the environment humidity to be 35-39%;
a3, placing the input end of the peristaltic pump into the spinning solution, setting the peristaltic rate of the peristaltic pump to be 0.96mL/h, and spinning for 4h to obtain the primary product of the electrostatic spinning fiber membrane.
Further, the preparation of the crude electrospun fiber membrane in the step S3 comprises the following operation steps:
b1, cutting silicone oil paper attached with an electrostatic spinning fiber membrane primary product into small pieces with the length of 4cm multiplied by 4cm, then laying the electrostatic spinning fiber membrane primary product on a tray, adding 10-20 parts by weight of absolute ethyl alcohol into the tray, then dripping 30-60 parts by weight of purified water into the tray, standing for 30-50 min, and taking out from the tray to obtain a soaked electrostatic spinning fiber membrane primary product;
and B2, weighing 30-60 parts of purified water according to parts by weight, placing the purified water on a tray, raising the temperature of the tray to 85-95 ℃, placing the immersed electrospun fiber film primary product on the tray, preserving heat for 10-12 h, taking out the electrospun fiber film primary product, and airing in a natural environment to obtain an electrospun fiber film crude product.
Further, the oscillator in the step S4 is a horizontal rotary shaking table, and after the oscillation is completed, the modified electrostatic spinning film is placed in absolute ethyl alcohol to be immersed for 10-14 hours, and naturally dried, so that an electrostatic spinning fiber film finished product is obtained.
The invention has the following beneficial effects:
1. in the preparation process of the electrostatic spinning fiber membrane, the polyvinyl alcohol is taken as a spinning aid, the electrostatic spinning fiber membrane can be rapidly molded in the preparation process through the electrostatic spinning equipment, and in the subsequent treatment process, the polyvinyl alcohol is washed out of the electrostatic spinning fiber membrane, so that the thickness of the electrostatic spinning fiber membrane is reduced, and before the polyvinyl alcohol is washed out of the electrostatic spinning fiber membrane, the initial product of the electrostatic spinning fiber membrane is soaked and solidified by using ethanol and water, so that the electrostatic spinning fiber is prevented from folding and deforming when the polyvinyl alcohol is soaked in hot water to wash out the electrostatic spinning fiber membrane, and the specific surface area of the electrostatic spinning fiber membrane is increased due to the fact that the polyvinyl alcohol is washed out, so that more metal particles can be adsorbed on the electrostatic spinning fiber membrane, the maximum adsorption capacity of the electrostatic spinning fiber membrane is improved, and the adsorption saturation time of the electrostatic spinning fiber membrane is reduced.
2. In the preparation process of the electrostatic spinning fiber membrane, the electrostatic spinning fiber membrane is modified, so that the electrostatic spinning fiber membrane has good reduction performance, and the gold and platinum in the wastewater are reduced into nano-scale particles after being adsorbed on the electrostatic spinning fiber membrane by combining the capability of chitosan for selectively adsorbing noble metals in the wastewater, and the adsorption capability of the electrostatic spinning fiber membrane on the noble metals is improved due to the fact that the electrostatic spinning fiber membrane has larger specific surface area, and the metals exist in the form of nano particles, so that the metals adsorbed on the electrostatic spinning fiber membrane can be recovered only through high-temperature firing during recovery, and the time and the technical cost for recovering the noble metals are greatly reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a block diagram of the process for preparing an electrospun fibrous membrane according to the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold elements in water comprises the following operation steps:
s1, preparing spinning solution:
weighing 0.4g of polyvinyl alcohol and 4.0g of purified water according to parts by weight, adding into a beaker, placing the beaker in a water bath environment with the temperature of 85 ℃, and stirring for 13 hours to completely dissolve the polyvinyl alcohol to obtain a polyvinyl alcohol solution;
weighing 0.2g of chitosan with the deacetylation degree higher than 99%, 5.0g of glacial acetic acid and 0.6g of purified water according to parts by weight, adding into a beaker, placing the beaker into a water bath environment with the temperature of 45 ℃, stirring for 9h, and dissolving chitosan to obtain a chitosan solution;
weighing 4.0g of polyvinyl alcohol solution, 6.0g of chitosan solution and 0.2g of octanol polyoxyethylene ether according to parts by weight, adding into a beaker, stirring, placing the beaker into a water bath environment with the temperature of 45 ℃, and stirring for 2.5h to obtain spinning solution;
s2, preparing an electrospun fibrous membrane primary product:
taking a stainless steel roller as a receiver, wrapping a layer of silicone paper outside the stainless steel roller, wherein the rotating speed of the stainless steel roller is 550rpm;
setting the spinning voltage to be 23.1kV, setting the distance between a spray head and a stainless steel roller to be 9cm, setting the environment temperature to be 23 ℃ and setting the environment humidity to be 35%;
placing the input end of a peristaltic pump into spinning solution, setting the peristaltic rate of the peristaltic pump to be 0.96mL/h, and spinning for 4h to obtain an electrostatic spinning fibrous membrane primary product;
s3, preparing a crude product of the electrostatic spinning fiber membrane:
cutting silicone oil paper attached with an electrostatic spinning fiber membrane primary product into small pieces of 4cm multiplied by 4cm, then taking the electrostatic spinning fiber membrane primary product off the silicone oil paper by using tweezers, laying the electrostatic spinning fiber membrane primary product on a tray, adding 100g of absolute ethyl alcohol into the tray, floating the electrostatic spinning fiber membrane primary product on the surface of the absolute ethyl alcohol, supporting the electrostatic spinning fiber membrane primary product to be unfolded, then dripping 300g of purified water into the tray, taking care that the electrostatic spinning fiber membrane primary product does not bend and fold in the process of dripping, standing for 30min after dripping is finished, taking the electrostatic spinning fiber membrane primary product out of the tray by using tweezers, and obtaining the immersed electrostatic spinning fiber membrane primary product;
300g of purified water is weighed according to parts by weight and added on a tray, the temperature of the tray is increased to 85 ℃, the immersed electrospun fibrous membrane primary product is laid on the tray, the temperature is kept for 10 hours, the dissolution of polyvinyl alcohol is promoted, the electrospun fibrous membrane primary product is taken out, and the electrospun fibrous membrane crude product is obtained after airing in natural environment.
S4, preparing an electrostatic spinning fiber membrane finished product:
placing the crude electrostatic spinning film in a beaker, adding 8g of 50wt% glutaraldehyde aqueous solution into the beaker, standing for 4 hours, pouring out the glutaraldehyde aqueous solution in the beaker, adding 8g of modified solution into the beaker, placing the beaker on a horizontal rotary shaking table with the model of HAD-SK3, oscillating for 4 hours, placing the modified electrostatic spinning film in 20g of absolute ethyl alcohol, immersing for 10 hours, and naturally airing to obtain an electrostatic spinning fiber film finished product.
The modified liquid is prepared by uniformly mixing 3.8g of absolute ethyl alcohol, 2.0g of 2.2wt% sulfuric acid solution, 2.0g of 2.5wt% thiourea solution and 0.2g of formaldehyde solution.
Example 2
The chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold elements in water comprises the following operation steps:
s1, preparing spinning solution:
weighing 0.6g of polyvinyl alcohol and 6.0g of purified water according to parts by weight, adding into a beaker, placing the beaker in a water bath environment with the temperature of 90 ℃, and stirring for 12 hours to completely dissolve the polyvinyl alcohol to obtain a polyvinyl alcohol solution;
weighing 0.3g of chitosan with the deacetylation degree higher than 99%, 8.1g of glacial acetic acid and 0.9g of purified water according to parts by weight, adding into a beaker, placing the beaker into a water bath environment with the temperature of 50 ℃, stirring for 8 hours, and dissolving chitosan to obtain a chitosan solution;
weighing 6.0g of polyvinyl alcohol solution, 9.0g of chitosan solution, 0.1g of laureth and 0.2g of octanol polyoxyethylene ether according to parts by weight, adding into a beaker, stirring, placing the beaker into a water bath environment with the temperature of 50 ℃, and stirring for 2.5h to obtain spinning solution;
s2, preparing an electrospun fibrous membrane primary product:
taking a stainless steel roller as a receiver, wrapping a layer of silicone paper outside the stainless steel roller, wherein the rotating speed of the stainless steel roller is 600rpm;
setting the spinning voltage to 23.1kV, setting the distance between a spray head and a stainless steel roller to 10cm, setting the environmental temperature to 26 ℃ and setting the environmental humidity to 37%;
placing the input end of a peristaltic pump into spinning solution, setting the peristaltic rate of the peristaltic pump to be 0.96mL/h, and spinning for 4h to obtain an electrostatic spinning fibrous membrane primary product;
s3, preparing a crude product of the electrostatic spinning fiber membrane:
cutting silicone oil paper attached with an electrostatic spinning fiber membrane primary product into small pieces of 4cm multiplied by 4cm, then taking the electrostatic spinning fiber membrane primary product off the silicone oil paper by using tweezers, laying the electrostatic spinning fiber membrane primary product on a tray, adding 140g of absolute ethyl alcohol into the tray, floating the electrostatic spinning fiber membrane primary product on the surface of the absolute ethyl alcohol, supporting the electrostatic spinning fiber membrane primary product to be unfolded, then dropwise adding 420g of purified water into the tray, paying attention to the electrostatic spinning fiber membrane primary product not to be bent and folded in the process of dropwise adding, standing for 40min after dropwise adding is completed, completely soaking the electrostatic spinning fiber membrane primary product, and taking the electrostatic spinning fiber membrane primary product out of the tray by using tweezers to obtain a soaked electrostatic spinning fiber membrane primary product;
and (3) weighing 420g of purified water according to parts by weight, adding the purified water into a tray, heating the tray to 90 ℃, placing the immersed electrospun fibrous membrane primary product on the tray, preserving heat for 12 hours, promoting the dissolution of polyvinyl alcohol, taking out the electrospun fibrous membrane primary product, and airing in a natural environment to obtain an electrospun fibrous membrane crude product.
S4, preparing an electrostatic spinning fiber membrane finished product:
placing the crude electrostatic spinning film in a beaker, adding 10g of 50wt% glutaraldehyde aqueous solution into the beaker, standing for 5h, pouring out the glutaraldehyde aqueous solution in the beaker, adding 10g of modified solution into the beaker, placing the beaker on a horizontal rotary shaking table with the model of HAD-SK3, oscillating for 5h, immersing the modified electrostatic spinning film in 25g of water ethanol for 12h, and naturally airing to obtain an electrostatic spinning fiber film finished product.
The modified liquid is prepared by uniformly mixing 4.8g of absolute ethyl alcohol, 2.5g of 2.2wt% sulfuric acid solution, 2.5g of 2.5wt% thiourea solution and 0.2g of formaldehyde solution.
Example 3
The chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold elements in water comprises the following operation steps:
s1, preparing spinning solution:
weighing 0.8g of polyvinyl alcohol and 8.0g of purified water according to parts by weight, adding into a beaker, placing the beaker in a water bath environment with the temperature of 95 ℃, and stirring for 11 hours to completely dissolve the polyvinyl alcohol to obtain a polyvinyl alcohol solution;
weighing 0.4g of chitosan with the deacetylation degree higher than 99%, 10.0g of glacial acetic acid and 1.2g of purified water according to parts by weight, adding into a beaker, placing the beaker into a water bath environment with the temperature of 55 ℃, stirring for 5 hours, and completely dissolving the chitosan to obtain a chitosan solution;
8.0g of polyvinyl alcohol solution, 12.0g of chitosan solution and 0.4g of octanol polyoxyethylene ether are weighed according to parts by weight, added into a beaker and stirred, the beaker is placed in a water bath environment with the temperature of 55 ℃ and stirred for 2.5h, and a spinning solution is obtained.
S2, preparing an electrospun fibrous membrane primary product:
taking a stainless steel roller as a receiver, wrapping a layer of silicone paper outside the stainless steel roller, wherein the rotating speed of the stainless steel roller is 650rpm;
setting the spinning voltage to be 23.1kV, setting the distance between a spray head and a stainless steel roller to be 11cm, setting the environment temperature to be 28 ℃ and setting the environment humidity to be 39%;
and placing the input end of the peristaltic pump into the spinning solution, setting the peristaltic rate of the peristaltic pump to be 0.96mL/h, and spinning for 4h to obtain the primary product of the electrostatic spinning fiber membrane.
S3, preparing a crude product of the electrostatic spinning fiber membrane:
cutting silicone oil paper attached with an electrostatic spinning fiber membrane primary product into small pieces of 4cm multiplied by 4cm, then taking the electrostatic spinning fiber membrane primary product off the silicone oil paper by using tweezers, laying the electrostatic spinning fiber membrane primary product on a tray, adding 180g of absolute ethyl alcohol into the tray, floating the electrostatic spinning fiber membrane primary product on the surface of the absolute ethyl alcohol, supporting the electrostatic spinning fiber membrane primary product to be unfolded, then dripping 540g of purified water into the tray, taking care that the electrostatic spinning fiber membrane primary product does not bend and fold in the process of dripping, standing for 50min after dripping is finished, taking the electrostatic spinning fiber membrane primary product out of the tray by using tweezers, and obtaining the immersed electrostatic spinning fiber membrane primary product;
and (3) weighing 540g of purified water according to parts by weight, adding the purified water onto a tray, raising the temperature of the tray to 95 ℃, placing the immersed electrospun fibrous membrane primary product onto the tray, preserving heat for 12 hours, promoting the dissolution of polyvinyl alcohol, taking out the electrospun fibrous membrane primary product, and airing in a natural environment to obtain an electrospun fibrous membrane crude product.
S4, preparing an electrostatic spinning fiber membrane finished product:
placing the crude electrostatic spinning film in a beaker, adding 12.0g of 50wt% glutaraldehyde water solution into the beaker, standing for 6 hours, pouring out the glutaraldehyde water solution in the beaker, adding 12.0g of modified solution into the beaker, placing the beaker on a horizontal rotary shaking table with the model of HAD-SK3 for shaking for 6 hours, immersing the modified electrostatic spinning film in 30g of absolute ethyl alcohol for 14 hours, and naturally airing to obtain an electrostatic spinning fiber film finished product;
the modified liquid is prepared by uniformly mixing 5.9g of absolute ethyl alcohol, 2.9g of 2.2wt% sulfuric acid solution, 2.9g of 2.5wt% thiourea solution and 0.3g of formaldehyde solution.
Comparative example 1
The difference between the comparative example and the example 3 is that the next treatment of the immersed electrospun fibrous membrane primary product in the step S3 is eliminated, and the immersed electrospun fibrous membrane primary product is directly and naturally dried to obtain a crude electrospun fibrous membrane product.
Comparative example 2
The difference between this comparative example and example 3 is that the step S4 is eliminated and the crude electrospun fiber film is directly used as a finished electrospun fiber film.
Comparative example 3
The comparative example is different from example 3 in that in step S3, the step of impregnating the cut-out electrospun fibrous membrane precursor was eliminated, and the electrospun fibrous membrane precursor was directly placed in a tray containing 540g of purified water for treatment.
Performance test:
the electrospun fiber membranes prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for adsorption saturation time, maximum adsorption capacity and adsorption efficiency, and the initial weight of the electrospun fiber membrane was recorded as m 1 Placing the electrostatic spinning fiber membrane into a simulation practical test solution prepared in advance, wherein the concentration of gold ions in the simulation practical test solution is 200ppb of ions of interference elements such as platinum, zinc, lead, nickel, copper and the like are additionally added, the pH=5 of an actual test solution is simulated, the initial ion concentration in the test solution and the final ion concentration record when the ion concentration of the test solution is no longer reduced are detected by ICP-OES, and the maximum adsorption capacity of the electrostatic spinning fiber membrane is obtained by calculating the difference value between the initial ion concentration and the final ion concentration; the adsorbed noble metal is refined through burning, the weight of the adsorbed noble metal is weighed, and the content of gold, platinum and other metals is detected through calculation, so that the adsorption efficiency of the electrostatic spinning fiber membrane to the noble metal is obtained. The specific detection results are shown in the following table:
the data analysis in combination with the above table shows that:
1) According to the detection data analysis of the embodiment 1-3, the prepared electrostatic spinning fiber membrane has good adsorption efficiency on gold in wastewater, the adsorption efficiency of gold reaches 97.3%, the recovery efficiency of platinum which is another common noble metal is 76.2%, and the recovery efficiency of platinum which is another non-noble metal is only 2.3%, which indicates that the recovery of gold in a water body is not influenced by the existence of the other non-noble metal elements, because the prepared electrostatic spinning fiber membrane has lower thickness and larger specific surface area, the maximum adsorption capacity of the membrane is improved, the electrostatic spinning fiber membrane is modified by the modifying liquid, and most of noble metals existing in the ionic form are reduced into nano-scale particles when the noble metals are attached to the outside of the membrane, and because the electrostatic spinning fiber membrane has larger specific surface area, the reduced metal particles can be adsorbed on the membrane, so that the adsorption efficiency of metals is improved.
2) Analysis of the detection data of comparative example 1 and example 3 shows that, since comparative example 1 eliminates the next treatment of the immersed electrospun fiber film primary product in step S3, the immersed electrospun fiber film primary product is directly and naturally dried to obtain an electrospun fiber film crude product, so that the polyvinyl alcohol in the electrospun fiber film cannot be separated from the electrospun fiber film, the polyvinyl alcohol wraps the chitosan fiber, the capacity of the electrospun fiber film capable of adsorbing wastewater and noble metals is reduced, the maximum adsorption capacity and adsorption saturation time of the electrospun fiber film in comparative example 1 are reduced, and since the polyvinyl alcohol wraps the chitosan, the modified liquid cannot be fused with the chitosan in step S4, the modification effect of the chitosan is poor, the adsorption interference of other interference noble metals in the wastewater on the electrospun fiber film is large, and the adsorption recovery efficiency of the electrospun fiber film on gold in the wastewater is low.
3) As is clear from the analysis of the detection data of comparative example 2 and example 3, since the step S4 is omitted in comparative example 2, the crude electrospun fiber film is directly used as a finished electrospun fiber film, when the electrospun fiber film adsorbs metals in wastewater, metals in the form of ions are adsorbed on the electrospun fiber film, and since the electrospun fiber film is not modified, metals adsorbed on the electrospun fiber are always in the form of ions and cannot be reduced into particles, so that when the electrospun fiber film is taken out from the wastewater, the wastewater is separated from the electrospun fiber film, and noble metals in the form of ions are separated from the electrospun fiber film along with the wastewater, so that a large amount of noble metal ions adsorbed on the electrospun fiber film are lost, and the recovery efficiency of the noble metals is low.
4) As is clear from the analysis of the detection data of comparative example 3 and example 3, in comparative example 3, the step of impregnating the cut electrospun fiber film precursor in step S3 is eliminated, the electrospun fiber film precursor is directly placed in a tray containing 540g of purified water for treatment, the content of the co-spinning agent polyvinyl alcohol in the electrospun fiber film precursor is higher, the polyvinyl alcohol in the electrospun fiber film precursor is directly contacted with water without the previous impregnating treatment, the polyvinyl alcohol in the electrospun fiber film precursor is rapidly dissolved in the water, the rapid shrinkage of the electrospun fiber film precursor is caused, the thickness of the electrospun fiber film precursor is increased, the specific surface area of the electrospun fiber film is reduced, the adsorption capacity of the electrospun fiber film is reduced, noble metals are easily separated from the electrospun fiber film in the adsorption process, the recovery efficiency of metals is lower, the permeability of the electrospun fiber film is reduced, the adsorption time of the electrospun fiber film is prolonged, and the specific surface area of the electrospun fiber film is reduced.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (6)
1. A chitosan-based electrostatic spinning fiber film capable of efficiently recovering gold element in water is characterized by comprising the following operation steps:
s1, weighing 20-30 parts of polyvinyl alcohol solution, 30-90 parts of chitosan solution and 1-2 parts of surfactant according to parts by weight, adding into a beaker, stirring, placing the beaker into a water bath environment with the temperature of 45-55 ℃, and stirring for 2-3 hours to obtain spinning solution;
s2, preparing an electrostatic spinning fiber membrane primary product by electrostatic spinning of the spinning solution;
s3, cutting and cleaning the primary product of the electrostatic spinning film to obtain a crude product of the electrostatic spinning fiber film;
s4, placing the electrostatic spinning film crude product in a beaker, adding 10-20 parts by weight of 50wt% glutaraldehyde water solution into the beaker, standing for 4-6 hours, pouring out the glutaraldehyde water solution in the beaker, adding 10-20 parts by weight of modified solution into the beaker, placing the beaker on an oscillator for oscillating for 4-6 hours, and cleaning to obtain an electrostatic spinning fiber film finished product, wherein the modified solution is prepared by uniformly mixing 50-100 parts by weight of absolute ethyl alcohol, 25-50 parts by weight of 2.2wt% sulfuric acid solution, 25-50 parts by weight of 2.5wt% thiourea solution and 2-4 parts by weight of formaldehyde solution;
and S3, preparing a crude product of the electrostatic spinning fiber membrane in the step of operation comprises the following steps:
b1, cutting silicone oil paper attached with an electrostatic spinning fiber membrane primary product into small pieces with the size of 4cm multiplied by 4cm, then laying the electrostatic spinning fiber membrane primary product on a tray, adding 10-20 parts by weight of absolute ethyl alcohol into the tray, then dripping 30-60 parts by weight of purified water into the tray, standing for 30-50 min, and taking out from the tray to obtain a soaked electrostatic spinning fiber membrane primary product;
and B2, weighing 30-60 parts of purified water according to parts by weight, placing the purified water on a tray, raising the temperature of the tray to 85-95 ℃, placing the immersed electrospun fiber film primary product on the tray, preserving heat for 10-12 h, taking out the electrospun fiber film primary product, and airing in a natural environment to obtain an electrospun fiber film crude product.
2. The chitosan-based electrospun fiber membrane capable of efficiently recovering gold element in water according to claim 1, wherein the preparation method of the polyvinyl alcohol solution in the step S1 is as follows: 2-6 parts of polyvinyl alcohol and 20-60 parts of purified water are weighed according to parts by weight, added into a beaker, placed in a water bath environment with the temperature of 85-95 ℃ and stirred for 10-14 hours, and the polyvinyl alcohol is dissolved, so that a polyvinyl alcohol solution is obtained.
3. The chitosan-based electrospun fiber membrane capable of efficiently recovering gold element in water according to claim 1, wherein the preparation method of the chitosan solution in the step S1 is as follows: 1-3 parts of chitosan, 25-85 parts of glacial acetic acid and 3-9 parts of purified water are weighed according to parts by weight, added into a beaker, placed in a water bath environment with the temperature of 45-55 ℃ and stirred for 6-10 hours, and chitosan is dissolved, so that a chitosan solution is obtained.
4. The chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold elements in water according to claim 1, wherein the surfactant in the step S1 is composed of one or more of octyl phenyl polyoxyethylene ether, lauryl polyoxyethylene ether, secondary alcohol polyoxyethylene ether and octanol polyoxyethylene ether, and the deacetylation degree of chitosan is more than 99%.
5. The chitosan-based electrospun fiber membrane capable of efficiently recovering gold element in water according to claim 1, wherein the electrospinning in step S2 comprises the following operation steps:
a1, taking a stainless steel roller as a receiver, wrapping a layer of silicone paper outside the stainless steel roller, wherein the rotating speed of the stainless steel roller is 550-650 rpm;
a2, setting the spinning voltage to be 23.1kV, setting the distance between a spray head and a stainless steel roller to be 9-11 cm, setting the environment temperature to be 23-28 ℃ and setting the environment humidity to be 35-39%;
a3, placing the input end of the peristaltic pump into the spinning solution, setting the peristaltic rate of the peristaltic pump to be 0.96mL/h, and spinning for 4h to obtain the primary product of the electrostatic spinning fiber membrane.
6. The chitosan-based electrostatic spinning fiber membrane capable of efficiently recovering gold elements in water according to claim 1, wherein the oscillator in the step S4 is a horizontal rotary shaking table, and after the oscillation is completed, the modified electrostatic spinning membrane is placed in absolute ethyl alcohol to be immersed for 10-14 h and naturally dried, so that an electrostatic spinning fiber membrane finished product is obtained.
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