CN116459810A - Underwater microplastic treatment method based on Ru-based difunctional aerogel - Google Patents
Underwater microplastic treatment method based on Ru-based difunctional aerogel Download PDFInfo
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- 229920000426 Microplastic Polymers 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 20
- 239000002737 fuel gas Substances 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 230000008929 regeneration Effects 0.000 claims abstract description 7
- 238000011069 regeneration method Methods 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 30
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- 239000007788 liquid Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 238000002835 absorbance Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 7
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2101/30—Organic compounds
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a method for treating microplastic in water based on Ru-based bifunctional aerogel, which adopts a reduction self-assembly method to induce and prepare Ru-based bifunctional aerogel, then treats the microplastic in water into fuel gas based on Ru-based bifunctional aerogel in a way of adsorption and thermocatalysis, solves the problem of difficult separation of graphene-based aerogel and adsorbate in the prior art, particularly realizes regeneration of reacted aerogel by means of plasma technology, and finally uses the obtained product in subsequent circulating treatment of microplastic in water, thereby solving the problems of high separation and regeneration cost of graphene-based aerogel in the prior art.
Description
Technical field:
the invention relates to a method for treating microplastic in water based on Ru-based difunctional aerogel.
The background technology is as follows:
microplastic is a new type of global environmental pollutant and is mainly composed of plastic fragments, films or particles with the particle size smaller than 5 mm. The environmental hazard of microplastics is emphasized by their particle size compared to "white contaminated" plastics. In water and soil, the high specific surface area and lipophilicity of the micro plastic cause the micro plastic to easily enrich heavy metals and organic matters, so that compound toxicity is generated, and the treatment cost and difficulty are greatly improved. In terms of distribution, microplastic pollution exists mainly in water bodies (particularly marine environment water bodies), and relatively little in soil and atmospheric environment. At present, with the mass use of plastic products, the scale of micro plastic pollution in water is continuously increased. Researchers have even found the presence of microplastic in the lungs of marine animals and humans. In recent years, research on microplastic is becoming a research hotspot in the environmental field. However, how to remove microplastic in the water environment is still in the starting stage.
Compared with the traditional method, the adsorption method has the advantages of high efficiency, low energy consumption, simple operation and the like, gradually becomes the supplement and perfection of the traditional water pollution control technology, and has wide application prospect. Currently, a variety of porous powder materials have been developed and successfully applied to microplastic removal in water, among which biochar, metal oxide/carbon composites, and metal organic framework materials are mainly used. It is noted that the problem of solid-liquid separation of these powder adsorbents after adsorption is not really solved. Meanwhile, the adsorbent remained in the water is easy to cause secondary pollution. Compared with other powder adsorption materials, the graphene-based aerogel block structure is safer and more environment-friendly in the aspect of environmental treatment, and is easy to separate and recycle. In practical applications, graphene-based aerogel cycle life is also an important consideration. Notably, in the current study of microplastic removal, patent (CN 110559995 a) discloses a method for adsorbing polystyrene microplastic in water using three-dimensional graphene. Although the three-dimensional graphene prepared in the patent can be used for adsorbing polystyrene microplastic in water, the degradation of the microplastic is not realized, and the problems that the adsorbent is difficult to separate from the substance to be adsorbed, the adsorption performance is attenuated and the like cannot be solved. How to separate carbon-based aerogel from microplastic at low cost has become a key issue for successful application in practice.
The invention comprises the following steps:
the invention aims to provide a method for treating microplastic in water based on Ru-based bifunctional aerogel, which adopts a reduction self-assembly method to induce and prepare Ru-based bifunctional aerogel, then treats the microplastic in water into fuel gas based on Ru-based bifunctional aerogel in a way of adsorption and thermocatalysis, solves the problem of difficult separation of graphene-based aerogel and adsorbate in the prior art, particularly realizes regeneration of aerogel after reaction by means of plasma technology, and finally uses the obtained product in subsequent recycling treatment of microplastic in water, thereby solving the problems of high separation and regeneration cost of graphene-based aerogel in the prior art.
The invention is realized by the following technical scheme:
a method for treating microplastic in water based on Ru-based bifunctional aerogel comprises the following steps:
1) The Ru-based bifunctional aerogel is prepared by adopting a reduction self-assembly method in an induction way: firstly, adding Ru salt and a reducing agent into graphene oxide dispersion liquid, carrying out ultrasonic treatment, heating to 70-150 ℃, reacting for a period of time, immersing into ethanol aqueous solution for dialysis, and then carrying out freeze drying treatment to obtain Ru-based bifunctional aerogel;
2) Adsorbing microplastic in water and converting the microplastic into fuel gas: adding the Ru-based bifunctional aerogel of step 1) to a micro-containing materialAdsorbing in water of plastic at normal temperature for a period of time, evaluating the treatment condition of microplastic in water by detecting absorbance in an adsorption system, drying the composite aerogel after adsorption is completed, transferring to a high-pressure reaction kettle, and controlling H 2 And (3) pressure and setting a heating program to perform C-C bond breaking reaction, and obtaining the fuel gas with high added value after the reaction is finished.
Preferably, in step 1), the Ru salt is Ru (NO) (NO 3 ) 3 、RuCl 3 ·3H 2 O、(NH 4 ) 2 RuCl 6 And [ Ru (NH) 3 ) 6 ]Cl 3 The reducing agent is one or more of ascorbic acid, ethylenediamine and hydrazine hydrate; the mass ratio of Ru salt to reducing agent to graphene is 1: (1-30), wherein the reaction time is 1-10 h, and the reaction temperature is 95-100 ℃.
In step 2), the microplastic comprises one or more of polyethylene, polyvinyl chloride and polypropylene; h 2 The pressure is 3-50 Mpa, the heating rate in the heat treatment is 1-10 ℃/min, the reaction temperature is 150-280 ℃, and the reaction time is 2-48 h.
In particular, the invention also comprises the following steps: regeneration of aerogel after reaction: after the Ru-based bifunctional aerogel is washed and dried, the Ru-based bifunctional aerogel is placed in a plasma reactor and is subjected to O 2 The power is controlled to be 50-120W in the atmosphere, residues on the surface of the Ru-based bifunctional aerogel can be removed after the reaction is carried out for 1-10min, the adsorption-thermal conversion performance of the Ru-based bifunctional aerogel can be recovered, and the Ru-based bifunctional aerogel is circularly used for adsorbing microplastic in water and converting the Ru-based bifunctional aerogel into fuel gas.
According to the invention, proper metal sites are regulated and controlled to enable the graphene-based aerogel to have hydrocracking capability, and the method plays an important role in separating micro plastics adsorbed on the surface of the carbon-based aerogel by adopting a thermal conversion method. In addition, during recycling, the aerogel adsorption interface environment is easy to change, and further performance attenuation is caused. For carbon-based aerogel, the active particles of the plasmas bombard the surface of a carbon material, so that the surface roughness of the carbon material is increased under the condition of not damaging the material body, meanwhile, chemical bonds of surface molecules of the carbon-based aerogel are opened, surface active groups are increased, and the changes are significant for improving the adsorption performance of the reacted aerogel and recovering the interface environment.
The beneficial effects of the invention are as follows:
1) The Ru-based bifunctional aerogel is prepared by adopting a reduction self-assembly method, and Ru metal is loaded in the reduction induction aerogel forming process; the process is simple and has high operability.
2) The Ru-based double-function aerogel can well adsorb micro-plastic particles in water, and can be converted into fuel gas with high added value in a subsequent thermocatalytic mode, so that the problem that an adsorbent and micro-plastic are difficult to separate is effectively solved; the process is a promising way of treating microplastic in water.
3) And the plasma technology is adopted to remove residues on the surface of the reacted Ru-based bifunctional aerogel, so that the adsorption-thermal conversion performance is recovered, and the recycling performance of the Ru-based bifunctional aerogel is improved.
Description of the drawings:
figure 1 is an XRD pattern of the material made in example 1.
Fig. 2 is an XPS diagram of the material made in example 1.
FIG. 3 shows the conversion of the material adsorption-thermocatalytic microplastic in water after regeneration with plasma treatment in example 1.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1: underwater micro-plastic circulation treatment technology based on Ru-based difunctional aerogel
Graphene oxide dispersions were prepared using the hummers method, reference (Carbon, 2013,64,225-229).
The method comprises the following steps:
step 1, preparing Ru-based bifunctional aerogel:
7mg (NH) 4 ) 2 RuCl 6 Directly dissolving in graphene oxide dispersion liquid (12 mL,3 mg/L), and stirring at normal temperature for 10h; subsequently, 72mg of ethylenediamine was added and sonicated for 30min; heating the dispersion liquid to 100 ℃ and then maintaining for 8 hours to form Ru-based composite hydrogel; immersing the hydrogel into BDialyzing the alcohol water solution for 36 hours; finally, the hydrogel is put into an ultralow temperature refrigerator for freezing, and then is subjected to freeze drying treatment, so that the Ru-based bifunctional aerogel can be obtained, and the crystal structure is shown in figure 1.
As shown in fig. 2, the prepared Ru-based bifunctional aerogel contains C, ru element, indicating that Ru has been successfully loaded into the aerogel.
Step 2, converting the micro plastic in water into fuel gas: 30mg of the obtained Ru-based bifunctional aerogel is placed in water containing polyethylene (20 mg/L) and stirred at a constant speed; adsorbing for 2h at normal temperature until the material reaches adsorption-desorption equilibrium for the micro plastic; then, collecting the composite aerogel and drying; finally, transferring the mixture into a high-pressure reaction kettle, and introducing H 2 Controlling the air pressure to be 30Mpa, heating to 250 ℃ at the heating rate of 10 ℃/min, and keeping for 16h; after cooling to room temperature, the final gaseous product was obtained. The degree of fracture of the target was evaluated by agilent gas chromatograph, and the results are shown in table 1.
TABLE 1
Table 1 shows that after 16h of high temperature reaction, the conversion of the microplastic polyethylene was completely converted into gas, up to 100%, where CH 4 The content is highest.
Referring to step 2, the performance of the obtained Ru-based bifunctional aerogel was investigated by replacing polyethylene with polypropylene or polyvinyl chloride microplastic shown in table 2, and the results are shown in table 2.
TABLE 2
As can be seen from Table 2, ru-based bifunctional aerogels also exhibit good adsorption-catalytic activity for other types of microplastic, and exhibit good selectivity for hydrocracking of C-C bonds.
After the Ru-based bifunctional aerogel is washed and dried after the reaction, the Ru-based bifunctional aerogel is placed in a plasma reactorAt O 2 The power is controlled to be 80W in the atmosphere, residues on the surface of the Ru-based bifunctional aerogel can be removed after the reaction is carried out for 5min, the adsorption-thermal conversion performance of the Ru-based bifunctional aerogel can be recovered, and the Ru-based bifunctional aerogel is circularly used for adsorbing polyethylene microplastic in water and converting the polyethylene microplastic into fuel gas. FIG. 3 is a graph showing the cycle performance of the Ru-based bifunctional aerogel prepared in this example. As shown in fig. 3, the composite aerogel showed good adsorption-catalytic life after each cycle using plasma treatment, with substantially unchanged conversion in four experiments.
Example 2: method for treating microplastic in water by adopting Ru-based difunctional aerogel
The method comprises the following steps:
step 1, preparing Ru-based bifunctional aerogel: 10mg of Ru (NO) (NO 3 ) 3 Directly dispersing in graphene oxide dispersion liquid (12 mL,3 mg/L), and stirring at normal temperature for 10h; 60mg of ascorbic acid was then added and sonicated for 30min; heating the dispersion liquid to 95 ℃ and then maintaining for 10 hours to form Ru-based composite hydrogel; immersing the hydrogel into ethanol water solution for dialysis for 36h; and finally, putting the hydrogel into an ultralow temperature refrigerator for freezing, and performing freeze drying treatment to obtain the Ru-based bifunctional aerogel.
Step 2, converting the micro plastic in water into fuel gas: referring to example 1, a polyethylene microplastic was used as a subject. The adsorption-catalysis performance of the prepared Ru-based bifunctional aerogel is explored. The results are shown in Table 1. After 16h of high temperature reaction, the conversion of the microplastic polyethylene is almost converted into gas, the conversion is up to 100%, wherein CH 4 The content is reduced compared with example 1.
Comparative example 1:
reference example 2 is different in that Ru (NO) (NO 3 ) 3
The step 1 is as follows: 72mg of ascorbic acid is completely dispersed in graphene oxide dispersion liquid (12 mL,3 mg/L), the graphene oxide dispersion liquid is heated to 95 ℃ and then kept for 10 hours, the hydrogel is immersed into ethanol water solution for dialysis for 36 hours, and then the graphene aerogel can be obtained through a freeze drying process.
Step 2 remained the same as in example 2. The results are shown in Table 1. As can be seen from table 1, graphene aerogel has little c—c bond hydrocracking ability.
The adsorption-catalytic properties of the microplastics obtained in examples 1, 2 and comparative example 1 were analyzed as shown in Table 1. From the results, the Ru-based bifunctional aerogel synthesized by the method provided by the invention adsorbs and catalyzes microplastic in water, and obtains high additional fuel gas. In addition, the composite aerogel shows good adsorption-catalytic life after each cycle by adopting plasma technology treatment, which has practical significance for the treatment of microplastic in water.
Claims (6)
1. The method for treating the microplastic in water based on the Ru-based bifunctional aerogel is characterized by comprising the following steps of:
1) The Ru-based bifunctional aerogel is prepared by adopting a reduction self-assembly method in an induction way: adding Ru salt and a reducing agent into graphene oxide dispersion liquid, performing ultrasonic treatment, heating to 70-150 ℃, reacting for a period of time, immersing into ethanol aqueous solution for dialysis, and performing freeze drying treatment to obtain Ru-based bifunctional aerogel;
2) Adsorbing microplastic in water and converting the microplastic into fuel gas: adding the Ru-based bifunctional aerogel in the step 1) into water containing microplastic, adsorbing for a period of time at normal temperature, evaluating the treatment condition of the microplastic in the water by detecting absorbance in an adsorption system, drying the composite aerogel after the adsorption is completed, transferring the composite aerogel to a high-pressure reaction kettle, and controlling H 2 And (3) pressure and setting a heating program to perform C-C bond breaking reaction, and obtaining the fuel gas with high added value after the reaction is finished.
2. The method of claim 1, wherein in step 1), the Ru salt is Ru (NO) (NO 3 ) 3 、RuCl 3 ·3H 2 O、(NH 4 ) 2 RuCl 6 And [ Ru (NH) 3 ) 6 ]Cl 3 The reducing agent is one or more of ascorbic acid, ethylenediamine and hydrazine hydrate.
3. The method for treating microplastic in water according to claim 1, wherein the mass ratio of Ru salt to reducing agent to graphene is 1: (1-30), wherein the reaction time is 1-10 h, and the reaction temperature is 95-100 ℃.
4. The method of treating microplastic in water according to claim 1, wherein in step 2), the microplastic comprises one or more of polyethylene, polyvinyl chloride and polypropylene.
5. The method for treating microplastic in water according to claim 1, wherein in the step 2), H is 2 The pressure is 3-50 Mpa, the heating rate in the heat treatment is 1-10 ℃/min, the reaction temperature is 150-280 ℃, and the reaction time is 2-48 h.
6. The method for treating microplastic in water according to claim 1, further comprising the steps of: regeneration of aerogel after reaction: after the Ru-based bifunctional aerogel is washed and dried, the Ru-based bifunctional aerogel is placed in a plasma reactor and is subjected to O 2 The power is controlled to be 50-120W in the atmosphere, residues on the surface of the Ru-based bifunctional aerogel can be removed after the reaction is carried out for 1-10min, the adsorption-thermal conversion performance of the Ru-based bifunctional aerogel can be recovered, and the Ru-based bifunctional aerogel is circularly used for adsorbing microplastic in water and converting the Ru-based bifunctional aerogel into fuel gas.
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| CN202310472397.3A CN116459810B (en) | 2023-04-27 | Underwater microplastic treatment method based on Ru-based difunctional aerogel |
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