CN109759135B - Preparation method of composite material for removing heavy metal/hydrophobic ppcps in reclaimed water - Google Patents
Preparation method of composite material for removing heavy metal/hydrophobic ppcps in reclaimed water Download PDFInfo
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Abstract
The invention discloses a preparation method of a composite material for removing heavy metal/hydrophobic ppcps in reclaimed water, which relates to a reclaimed water advanced treatment technology, and specifically comprises the following steps: 1) synthesizing nano cuprous oxide by a hydrothermal method; 2) synthesizing the temperature-sensitive carboxymethyl cyclodextrin-Cu by using the nano-cuprous oxide prepared in the step 1) through a one-step method2And (3) an O composite material. The method reduces the agglomeration phenomenon of the photocatalyst caused by small particle size, promotes the photocatalytic degradation efficiency, improves the mineralization rate of ppcps, enhances the dispersibility of the material because the introduced temperature-sensitive material poly-N-isopropylacrylamide is positioned at the outermost layer of the composite material, is beneficial to the photocatalytic reaction and adsorption, realizes the complete shrinkage and sedimentation performance of the composite material under the high temperature condition, and realizes the recovery of the catalyst through temperature control.
Description
Technical Field
The invention relates to a technology for deeply treating reclaimed water, in particular to a preparation method of a composite material for efficiently removing heavy metal/hydrophobic ppcps in reclaimed water.
Background
The medicines and personal care products (PPCPs) are novel micro-pollutants, have the characteristics of environmental stability, difficult degradability, biological accumulation and the like, and can cause irreversible potential harm to human health and ecological environment after long-term contact, so that the development of the technology for removing the PPCPs in reclaimed water has important theoretical and practical significance for the continuous development of the recycling industry of urban sewage in China. In addition, heavy metals, particularly nickel, chromium, cadmium, lead, mercury, and the like, which are directly and indirectly discharged into water from industries such as metal plating, mining, chemical fertilizers, or paper making, are often carcinogenic and bioaccumulative, interfere with physiological functions of living tissues, and are currently considered to be the priority environmental pollutants.
Because the traditional biological treatment technology of the urban sewage treatment plant has limited removal effect on PPCPs, related researches are carried out around advanced oxidation, membrane filtration, activated carbon adsorption and combined process methods at home and abroad in recent years. The advanced oxidation technology (AOPs) realizes the complete degradation of PPCPs or improves the biodegradability of the PPCPs through the strong oxidizing property of free radicals (mainly OH), wherein the photocatalyst technology is widely applied, the technology has a good removing effect on trace pollutants, but the agglomeration phenomenon of the ultrafine photocatalyst in a solution is an important factor influencing the photocatalytic effect. The adsorption is an efficient and feasible PPCPs removal technology, has low cost, easy operation, no byproduct generation and higher removal efficiency, but the effective recovery of the adsorbent is the problem to be solved.
Disclosure of Invention
In order to solve the problems, the invention aims to successfully prepare the composite material capable of effectively removing the heavy metals and the hydrophobic ppcps in the reclaimed water, and the composite material can realize temperature control recovery through modification of the temperature-sensitive material.
The preparation method of the composite material for removing heavy metal/hydrophobic ppcps in the reclaimed water comprises the following steps:
1) synthesizing nano cuprous oxide by a hydrothermal method;
2) synthesizing temperature-sensitive carboxymethyl cyclodextrin-Cu by using the nano cuprous oxide prepared in the step 1) through a one-step method2And (3) an O composite material.
The step 1) is specifically as follows: and (3) uniformly mixing the copper sulfate solution and the sodium hydroxide solution, adding an excessive ascorbic acid solution, magnetically stirring, fully and uniformly mixing, placing in a reaction kettle for reaction, and separating a solid product to obtain the nano cuprous oxide. The concentration of the NaOH solution is 5mol/L, and the CuSO4The concentration of the solution was 1mol/L and the concentration of the ascorbic acid solution was 1.5 mol/L. The CuSO4The molar ratio of NaOH to ascorbic acid is 1:15 (2-2.5). The reaction temperature is 120-135 ℃, the reaction pressure is 1.2-2.0MPa, and the reaction time is 8-12 h. The separated solid product is specifically as follows: filtering to obtain residue, sequentially washing with anhydrous ethanol and distilled water for 3-5 times, and vacuum drying. The vacuum drying is carried out, the vacuum degree is 1200 and 4800Pa, and the temperature is 55The temperature is 60 ℃ below zero for 2 to 20 hours.
And 2) specifically, dispersing the nano cuprous oxide prepared in the step 1) in distilled water, adding carboxymethyl cyclodextrin, poly-N-isopropyl acrylamide and sodium bisulfite, performing magnetic stirring reaction, performing ultrasonic dispersion to obtain a suspension, and separating and purifying to obtain a composite material for removing heavy metal/hydrophobic ppcps in the regenerated water, wherein the mass ratio of the nano cuprous oxide to the carboxymethyl cyclodextrin to the poly-N-isopropyl acrylamide is 5 (2-3) to (2-3), the mass ratio of the sodium bisulfite to the nano cuprous oxide is 1:2-2:1, the concentration of the nano cuprous oxide in the distilled water is 0.05-1g/mL, the reaction is performed under the conditions of ice water bath and nitrogen protection for 40-52h, the cyclodextrin in the carboxymethyl cyclodextrin is α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin, the separation and purification are specifically, the supernatant is removed by centrifugation, the precipitate is cleaned by deionized water for 3-5 times, the vacuum drying is performed at low temperature, the vacuum degree is 4800-1200 ℃, and the drying temperature is 20-1200 ℃.
Advantageous effects
The cuprous oxide composite material with considerable load of carboxymethyl cyclodextrin and poly-N-isopropylacrylamide is prepared by adopting a one-step method, carboxymethyl in the carboxymethyl cyclodextrin and heavy metal form a coordination compound, hydrophobic cavities of the cyclodextrin can efficiently envelop and retain hydrophobic ppcps, the carboxymethyl cyclodextrin interacts with a photocatalyst, the recombination probability of photo-generated electrons and holes is reduced, the structure of the surface of the photocatalyst is changed, the agglomeration phenomenon of the photocatalyst due to small particle size is reduced, the photocatalytic degradation efficiency is promoted, the mineralization rate of the ppcps is improved, the introduced temperature-sensitive material poly-N-isopropylacrylamide is positioned at the outermost layer of the composite material, the dispersibility of the material is enhanced, the photocatalytic reaction and adsorption can be favorably carried out, and the complete shrinkage and sedimentation performance of the composite material under the high-temperature condition can be realized, the catalyst can be recovered through temperature control.
Specifically, the method comprises the following steps:
1) on the basis of mature preparation of the photocatalyst nano cuprous oxide, the invention considers that the one-step method is adopted to introduce the carboxymethyl cyclodextrin with the coordination function and the enveloping function and the temperature-sensitive material poly N-isopropylacrylamide with mature application in the temperature-sensitive direction into the field of photocatalysis.
2) According to the composite material for efficiently removing the heavy metal/hydrophobic ppcps in the reclaimed water, the carboxymethyl cyclodextrin has the functions of adsorbing the heavy metal and enveloping the hydrophobic ppcps, wherein the carboxymethyl and the heavy metal form a coordination compound, and the hydrophobic cavity of the cyclodextrin can efficiently envelop and retain the hydrophobic ppcps, so that the efficient degradation of the ppcps and the entrapment and removal of the heavy metal can be realized simultaneously.
3) According to the composite material for efficiently removing heavy metal/hydrophobic ppcps in reclaimed water, the carboxymethyl cyclodextrin interacts with the surface of a photocatalyst through hydrogen bonds, so that photo-induced holes generated by the catalyst are guided to oxidize and degrade the hydrophobic ppcps enveloped in the cyclodextrin, and the recombination probability of photo-induced electrons and holes is reduced; meanwhile, the carboxymethyl cyclodextrin is adsorbed on the surface of the cuprous oxide photocatalyst, so that the structure of the surface of the photocatalyst is changed, the agglomeration phenomenon of the photocatalyst caused by small particle size is reduced, the photocatalytic degradation efficiency is promoted under the combined action, and the mineralization rate of ppcps is increased.
4) According to the composite material for efficiently removing the heavy metals/hydrophobic ppcps in the reclaimed water, the temperature-sensitive material poly-N-isopropylacrylamide in the material is positioned on the outermost layer of the composite material, so that the dispersibility of the material is enhanced, and the photocatalytic reaction and the adsorption can be favorably carried out; meanwhile, the volume of the material is reduced under the high-temperature condition, and the material can be completely shrunk and settled, so that the catalyst can be recovered by temperature control.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of a composite material for efficiently removing heavy metals/hydrophobic ppcps in reclaimed water comprises a photocatalyst cuprous oxide, carboxymethyl cyclodextrin and a temperature sensitive material poly-N-isopropyl acrylamide, and specifically comprises the following steps:
1) synthesizing nano cuprous oxide by a hydrothermal method: mixing a certain amount of copper sulfate solution and sodium hydroxide solution uniformly, adding excessive ascorbic acid solution (NaOH solution with concentration of 5mol/L, CuSO)4The concentration of the solution was 1mol/L and the concentration of the ascorbic acid solution was 1.5 mol/L. CuSO4NaOH and ascorbic acid in a molar ratio of 1:15:2), magnetically stirring, uniformly mixing, placing in a reaction kettle, reacting at high temperature and high pressure for 8h (120 ℃, 1.2MPa), filtering the solution, sequentially washing with ethanol and distilled water for 3 times, and placing in a vacuum drying oven for drying (the vacuum degree is 1200pa, the temperature is 55 ℃, and the time is 2 h). 2) One-step method for synthesizing temperature-sensitive carboxymethyl cyclodextrin-Cu2O composite material: dispersing a certain amount of cuprous oxide in a flask containing distilled water, adding a certain amount of carboxymethyl cyclodextrin, poly-N-isopropyl acrylamide and sodium bisulfite (the mass ratio of nano cuprous oxide to carboxymethyl cyclodextrin to poly-N-isopropyl acrylamide is 5: 2: 2; the mass ratio of sodium bisulfite to nano cuprous oxide is 1: 2; the concentration of nano cuprous oxide in distilled water is 0.05g/mL), magnetically stirring for 40 hours under the protection of ice water bath and nitrogen, ultrasonically dispersing into suspension, centrifuging, removing the unreacted reactant of the supernatant, washing with deionized water for 3 times, and drying the product at low temperature in vacuum (the vacuum degree is 1200pa, the drying temperature is 30 ℃, and the time is 2 hours) to obtain the composite material;
the cyclodextrin is α -cyclodextrin.
The prepared composite material (0.1g) was used for degrading 0.02mg/L galaxolide solution and 0.02mg/L heavy metal (pb, cd, Ni) containing solution (100mL), and the solutions were placed in natural light at 25 ℃ for reaction, and the removal rates of galaxolide and heavy metal were respectively 94%, 82%, 86% and 89% after 12 h. The composite material is subjected to photocatalytic performance test, the composite material reaches adsorption balance under a dark condition before the experiment, then the composite material is subjected to illumination treatment under the same condition, the removal rate of the galaxolide and the heavy metal is improved by about 1.23 times and 1.09 times by the aid of the cuprous oxide serving as the photocatalyst, and meanwhile, types of small molecular organic matters in a water body are remarkably increased by 1.3 times compared with the catalytic efficiency of the cuprous oxide serving as the single photocatalyst. After 12h, controlling the water temperature to be about 40 ℃, gradually shrinking the composite material from the dissolved colorless transparent body, completely shrinking and settling for about 15-20min, centrifugally recycling, and drying to obtain the recovery rate of about 88%. The example shows that the material has the functions of efficiently enriching the galaxolide and the heavy metal and degrading the galaxolide by photocatalysis; meanwhile, the composite material can realize material recovery through temperature control.
Example 2
A preparation method of a composite material for efficiently removing heavy metals/hydrophobic ppcps in reclaimed water comprises a photocatalyst cuprous oxide, carboxymethyl cyclodextrin and a temperature sensitive material poly-N-isopropyl acrylamide, and specifically comprises the following steps: 1) synthesizing nano cuprous oxide by a hydrothermal method: mixing a certain amount of copper sulfate solution and sodium hydroxide solution uniformly, adding excessive ascorbic acid solution (NaOH solution with concentration of 5mol/L, CuSO)4The concentration of the solution was 1mol/L and the concentration of the ascorbic acid solution was 1.5 mol/L. CuSO4And the molar ratio of NaOH to ascorbic acid is 1:15:2.5), the mixture is placed in a reaction kettle for high-temperature high-pressure reaction for 10 hours (135 ℃ and 2.0MPa) after being stirred and mixed fully by magnetic force, the solution is taken out for filtration, and is sequentially washed for 5 times by ethanol and distilled water respectively, and then is placed in a vacuum drying oven for drying (the degree of hollowness is 4800pa, the temperature is 60 ℃ and the time is 20 hours). 2) One-step method for synthesizing temperature-sensitive carboxymethyl cyclodextrin-Cu2O composite material: dispersing a certain amount of cuprous oxide in a flask containing distilled water, adding a certain amount of carboxymethyl cyclodextrin, poly-N-isopropyl acrylamide, and sodium bisulfite (nano cuprous oxide, carboxymethyl cyclodextrin, poly-N-isopropyl acrylamide)The mass ratio of (A) to (B) is 5: 3: 3; the mass ratio of the sodium bisulfite to the nano cuprous oxide is 2: 1; the concentration of the nano cuprous oxide in distilled water is 0.5g/mL), under the protection of ice water bath and nitrogen, magnetically stirring for 52h and ultrasonically dispersing into turbid liquid, centrifuging, removing unreacted substances in the supernatant, washing for 5 times by deionized water, and drying the product in vacuum at low temperature (the vacuum degree is 4800pa, the drying temperature is 40 ℃, and the drying time is 20h) to obtain the composite material.
The cyclodextrin is β -cyclodextrin.
The prepared composite material (0.1g) is used for degrading a mixed solution (100mL) of 5 mu g/L of galaxolide and diclofenac and 0.02mg/L of heavy metal (pb, cd, Ba), the mixed solution is placed in natural light at the temperature of 25 ℃ for reaction, the removal rates of the galaxolide and the heavy metal after 12h are respectively 94%, 82%, 84% and 90%, and the removal rate of the hydrophilic diclofenac is only 56%. The composite material is subjected to a photocatalytic performance test, the composite material reaches adsorption balance under a dark condition before an experiment, then the composite material is subjected to illumination treatment under the same condition, the removal rate of the galaxolide and the heavy metal is improved by about 1.24 times and 1.05 times by the aid of the cuprous oxide serving as a photocatalyst, and meanwhile, types of small molecular organic matters in a water body are remarkably increased by 1.3 times compared with the catalytic efficiency of the cuprous oxide serving as a single photocatalyst. After 12h, controlling the water temperature to be about 38 ℃, gradually shrinking the composite material from the dissolved colorless transparent body, completely shrinking and settling for about 15-20min, centrifugally recycling, and drying to obtain the recovery rate of about 90%. The embodiment shows that the material has the functions of efficiently enriching the galaxolide and the heavy metal and degrading the galaxolide by photocatalysis, and has better treatment effect on hydrophobic organic matters ppcps; meanwhile, the composite material can realize material recovery through temperature control.
Example 3
A preparation method of a composite material for efficiently removing heavy metals/hydrophobic ppcps in reclaimed water comprises a photocatalyst cuprous oxide, carboxymethyl cyclodextrin and a temperature sensitive material poly-N-isopropyl acrylamide, and specifically comprises the following steps: 1) synthesizing nano cuprous oxide by a hydrothermal method: mixing a certain amount of copper sulfate solution and sodium hydroxide solutionAfter mixing well, add excess ascorbic acid solution (NaOH solution concentration 5mol/L, CuSO)4The concentration of the solution was 1mol/L and the concentration of the ascorbic acid solution was 1.5 mol/L. CuSO4And the molar ratio of NaOH to ascorbic acid is 1:15:2.2), the mixture is placed in a reaction kettle for high-temperature high-pressure reaction for 10 hours (130 ℃, 1.7MPa) after being stirred and mixed evenly by magnetic force, the solution is filtered, and is sequentially washed by absolute ethyl alcohol and distilled water for 4 times, and then is placed in a vacuum drying oven for drying (the conditions are the same as those in the example 1). 2) One-step method for synthesizing temperature-sensitive carboxymethyl cyclodextrin-Cu2O composite material: dispersing a certain amount of cuprous oxide in a flask containing distilled water, adding a certain amount of carboxymethyl cyclodextrin, poly-N-isopropyl acrylamide and sodium bisulfite (the mass ratio of nano cuprous oxide to carboxymethyl cyclodextrin to poly-N-isopropyl acrylamide is 5: 3: 3; the mass ratio of sodium bisulfite to nano cuprous oxide is 1: 1; the concentration of nano cuprous oxide in distilled water is 0.8g/mL), magnetically stirring for 45 hours under the protection of ice water bath and nitrogen, ultrasonically dispersing into suspension, centrifuging, removing unreacted reactant in supernatant, washing with deionized water for 4 times, and drying the product in vacuum at low temperature (the conditions are the same as those in example 1) to obtain the composite material.
In particular, the cyclodextrin is gamma-cyclodextrin.
The prepared composite material (0.1g) is used for degrading 0.02mg/L tonalid solution and solution (100mL) containing 0.02mg/L heavy metal (pb, cd, Ni), the solution is placed in natural light at the temperature of 25 ℃ for reaction, and the removal rates of tonalid and heavy metal after 12h are respectively 93%, 82%, 86% and 89%. The composite material is subjected to photocatalytic performance test, the composite material reaches adsorption balance under a dark condition before the experiment, then the composite material is subjected to illumination treatment under the same condition, the removal rate of tonalid and heavy metal is improved by about 1.23 times and 1.09 times by using the photocatalyst cuprous oxide, and meanwhile, the types of small molecular organic matters in the water body are obviously increased, and the catalytic efficiency is improved by 1.3 times compared with that of the single photocatalyst cuprous oxide. After 12h, controlling the water temperature to be about 40 ℃, gradually shrinking the composite material from the dissolved colorless transparent body, completely shrinking and settling for about 15-20min, centrifugally recycling, and drying to obtain the recovery rate of about 90%. The example shows that the material has the functions of efficiently enriching tonalid and heavy metal and degrading tonalid through photocatalysis; meanwhile, the composite material can realize material recovery through temperature control.
Claims (12)
1. A preparation method of a composite material for removing heavy metal/hydrophobic ppcps in reclaimed water is characterized by comprising the following steps: the method comprises the following steps:
1) synthesizing nano cuprous oxide by a hydrothermal method;
2) synthesizing temperature-sensitive carboxymethyl cyclodextrin-Cu by using the nano cuprous oxide prepared in the step 1) through a one-step method2An O composite material;
wherein, the step 1) is specifically as follows: uniformly mixing a copper sulfate solution and a sodium hydroxide solution, adding an excessive ascorbic acid solution, magnetically stirring, fully and uniformly mixing, placing in a reaction kettle for reaction, and separating a solid product to obtain nano cuprous oxide;
the step 2) is specifically as follows: dispersing the nano cuprous oxide prepared in the step 1) in distilled water, then adding carboxymethyl cyclodextrin, poly-N-isopropyl acrylamide and sodium bisulfite, magnetically stirring to react, ultrasonically dispersing into suspension, separating and purifying to obtain the composite material with the heavy metal/hydrophobic ppcps removed from the reclaimed water.
2. The method for preparing the composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 1, wherein the method comprises the following steps: the concentration of the sodium hydroxide solution is 5mol/L, the concentration of the copper sulfate solution is 1mol/L, and the concentration of the ascorbic acid solution is 1.5 mol/L.
3. The method for preparing the composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 1, wherein the method comprises the following steps: the molar ratio of the copper sulfate, the sodium hydroxide and the ascorbic acid is 1:15 (2-2.5).
4. The method for preparing the composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 1, wherein the method comprises the following steps: the reaction in the reaction kettle in the step 1) is carried out at the reaction temperature of 120-.
5. The method for preparing the composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 1, wherein the method comprises the following steps: the separated solid product is specifically as follows: filtering to obtain residue, sequentially washing with anhydrous ethanol and distilled water for 3-5 times, and vacuum drying.
6. The method for preparing the composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 5, wherein the method comprises the following steps: the vacuum drying is carried out, the vacuum degree is 1200 and 4800Pa, the temperature is 55-60 ℃, and the time is 2-20 h.
7. The method for preparing the composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 1, wherein the method comprises the following steps: the mass ratio of the nano cuprous oxide to the carboxymethyl cyclodextrin to the poly N-isopropylacrylamide is 5: (2-3): (2-3).
8. The method for preparing the composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 1, wherein the method comprises the following steps: the mass ratio of the sodium bisulfite to the nano cuprous oxide is 1:2-2: 1; the concentration of the nano cuprous oxide in the distilled water is 0.05-1 g/mL.
9. The method for preparing the composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 1, wherein the method comprises the following steps: and 2) carrying out magnetic stirring reaction in the step 2), wherein the reaction is carried out under the conditions of ice water bath and nitrogen protection for 40-52 h.
10. The method for preparing the composite material for removing the heavy metal/hydrophobic ppcps in the reclaimed water according to claim 1, wherein the cyclodextrin in the carboxymethyl cyclodextrin is one of α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin.
11. The method for preparing the composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 1, wherein the method comprises the following steps: the separation and purification specifically comprises the following steps: centrifuging to remove supernatant, washing the precipitate with deionized water for 3-5 times, and vacuum drying at low temperature.
12. The method for preparing a composite material for removing heavy metals/hydrophobic ppcps in reclaimed water according to claim 11, wherein the method comprises the following steps: the low-temperature vacuum drying is carried out, the vacuum degree is 1200-4800Pa, the drying temperature is 30-40 ℃, and the drying time is 2-20 h.
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