CN115090237A - Method for converting zero-valent iron into waste plastic through photo-thermal conversion into high-value-added fuel and environment-repairing material - Google Patents
Method for converting zero-valent iron into waste plastic through photo-thermal conversion into high-value-added fuel and environment-repairing material Download PDFInfo
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- CN115090237A CN115090237A CN202210551688.7A CN202210551688A CN115090237A CN 115090237 A CN115090237 A CN 115090237A CN 202210551688 A CN202210551688 A CN 202210551688A CN 115090237 A CN115090237 A CN 115090237A
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/127—Sunlight; Visible light
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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- B01J35/39—
-
- B01J35/393—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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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
- 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 relates to a method for photothermal conversion of waste plastics into high value-added fuel and environment restoration materials by utilizing an oxygen-containing acid radical modified zero-valent iron material as a catalyst for photothermal conversion of the waste plastics, wherein the oxygen-containing acid radical modified zero-valent iron material has a micro-scale and/or nano-scale irregular granular micro-morphology structure, and surface species comprise boric acid and phosphate radicals. Compared with the prior art, the invention is used for converting waste plastics into high value-added fuel and environment repair materials by photo-thermal catalysis, the conversion rate of gaseous hydrocarbon products can reach more than 53 percent, and the stability is better. Meanwhile, the residual iron-carbon solid can be used as an environment restoration material, organic pollutants and heavy metals in underground water and soil can be efficiently removed, and higher efficiency can be maintained for a long time.
Description
Technical Field
The invention relates to the technical field of environmental catalysis, in particular to a method for converting waste plastics into high value-added fuel and environmental remediation material by using zero-valent iron through photo-thermal conversion.
Background
In recent years, the widespread accumulation of waste plastic masses and particulates in landfill areas and natural environments has received increasing attention worldwide, such as soil, rivers, oceans, mountains, polar regions, and the atmosphere. Waste plastics are stable in the environment for centuries due to their difficulty in biodegradation, presenting an immeasurable potential threat to wild/marine life as well as humans. The current plastic crisis comes from the plastic production and consumption speeds far exceeding the waste plastic recycling speed. The shortage of waste plastic resource not only causes the loss of the value chain of the petrochemical industry, but also brings serious threats to the energy, environment and climate safety. Therefore, a revolutionary new method integrating high efficiency, environmental protection and low carbon is urgently needed to be developed to realize large-scale recycling of waste plastics. The chemical method can gasify the waste plastics to convert the waste plastics into high-quality monomers and carbon materials, for example, the waste plastics are pyrolyzed into naphtha and charcoal under anaerobic condition, the partially oxidized and gasified waste plastics are industrial synthesis gas, and the waste plastics are depolymerized into monomers with the aid of a solvent. The chemical method has the greatest advantages that the fine pre-classification is not needed, the long-chain plastic can be directly subjected to chain scission in one pot, the product quality is high, and the method has a large-scale application foundation. Therefore, the large-scale chemical recovery process is considered as the most promising plastic resource approach and is expected to become a secondary engine for economic growth and carbon emission reduction under the background of sustainable development. However, the molecular structure of the plastic has extremely strong C-H, C-O, C-S and C-Cl bonds, and the plastic can be effectively broken only when the reaction temperature is close to 800 ℃. This leads to the consumption of a large amount of fossil energy in the current chemical recycling process of waste plastics, and fails to meet the target requirement of "double carbon", which may lead to the subsidy of money before "double carbon" and the abatement of damp, so that the processes such as pyrolysis, gasification and depolymerization cannot be profitable. In addition, conventional chemical processes also require high pressure, additional solvents or chemicals, and product selectivity also presents serious challenges. These problems have limited the scale-up of chemical processes, leaving less than three million tons of waste plastics currently recovered by chemical routes worldwide each year. Therefore, catalytic chemistry methods that meet new environmental protection and carbon emission requirements are still in the beginning. In particular, catalytic chemistry involves two core components, a catalyst and a catalytic driving force. The currently adopted catalytic method takes a micro/nano material as a catalyst, the catalyst has the advantages of high activity and controllable and adjustable product, and compared with non-catalytic thermal cracking at 800 ℃, the catalytic reaction temperature is reduced to about 500 ℃, but a large amount of fossil energy still needs to be consumed to provide driving force.
Photothermal catalysis is an efficient solar-driven zero-carbon or negative-carbon catalysis mode, and is mainly applied to a carbon conversion and utilization process after carbon capture. The photo-thermal catalysis is characterized in that low-energy-barrier photochemistry and non-equilibrium thermochemistry are further introduced on the basis of thermal catalysis, and the selectivity and yield of reaction products are improved by optimizing reaction kinetics and thermodynamics. More importantly, the catalytic driving force of photo-thermal catalysis is clean and renewable solar energy, so that the problems of energy consumption and carbon footprint of fossil energy are fundamentally solved. Meanwhile, the photothermal catalysis does not involve any water or organic solvent, the catalysis process is anaerobic catalysis, no sewage and virulent dioxin are generated, secondary environmental pollution is avoided, and a new way with low price, high efficiency and environmental protection is provided for carbon neutralization and waste plastic recycling. The photothermal catalyst is typically a metal and support composite. The metal composition is mostly Ag, Cu, Al and traditional transition metal with plasma resonance effect, and the source of the carrier material is very wide, including light inert white material (SiO) 2 And Al 2 O 3 ) Conventional semiconductor photocatalysts (e.g. TiO) 2 、ZnO、In 2 O 3 、NiO x And layered double hydroxide LDHs), conventional thermocatalytically active supports (such as metal hydrides, nitrides, carbides, phosphides, oxides, hydroxides, and composites thereof). However, the most advancedThe catalyst of (2) still inevitably forms severe carbon deposit-carbon material or metal-carbon composite after long-time operation, thereby causing rapid degradation of catalytic performance. The development of inexpensive and efficient photothermal catalysts to convert waste plastics into gaseous hydrocarbons with high added value is therefore a formidable challenge.
Disclosure of Invention
The invention aims to provide a method for converting waste plastics into high value-added fuel and environment-repairing materials by using zero-valent iron through photothermal conversion.
The purpose of the invention can be realized by the following technical scheme: an oxyacid radical modified zero-valent iron material is used as a catalyst to carry out photothermal conversion on the waste plastics, the oxyacid radical modified zero-valent iron material has a micro-scale and/or nano-scale irregular granular microstructure, and surface species comprise boric acid and phosphate radicals.
Preferably, the boric acid mass content of the surface of the oxygen acid radical modified zero-valent iron material is 0.05-6.18%.
Further preferably, the boric acid mass content of the surface of the oxygen acid radical modified zero-valent iron material is 0.5-3.65%.
Preferably, the mass content of the phosphate radical on the surface of the oxygen-containing radical modified zero-valent iron material is 0.01-3.53%.
Further preferably, the mass content of phosphate on the surface of the oxygen-containing acid radical modified zero-valent iron material is 0.2-2.18%.
Preferably, the diameters of the particles with the micron-scale size are all between 0.5 and 10 mu m, and the diameters of the particles with the nano-scale size are all between 80 and 800 nm.
Further preferably, the diameters of the particles with the micron-scale size are all between 0.5 and 4 mu m, and the diameters of the particles with the nano-scale size are all between 80 and 300 nm.
Preferably, the preparation method of the oxygen-containing acid radical modified zero-valent iron material comprises the following steps:
1) mixing the precursor containing the oxygen acid radical with zero-valent iron to obtain solid powder;
2) and mechanically ball-milling the solid powder in an inert atmosphere, and collecting the obtained product after naturally cooling to room temperature to obtain the oxygen-containing acid radical modified zero-valent iron material.
Further preferably, the oxide-containing precursor in step 1) is boric acid and phosphate.
Further preferably, the zero-valent iron is commercial iron powder, and the mechanical ball milling is to perform surface modification treatment on the commercial iron powder in a co-ball milling mode with boric acid and phosphate.
Further preferably, the rotation speed of the mechanical ball milling in the step 2) is 100-500 rpm, and the ball milling time is 1-6 hours.
Further preferably, the inert atmosphere in step 2) is nitrogen or argon.
Preferably, the method for converting the zero-valent iron photothermal waste plastics into high value-added fuels and environment restoration materials specifically comprises the following steps: in a sapphire window high-pressure hydrothermal reactor, a micron-scale and/or nano-scale zero-valent iron material modified by oxygen-containing boric acid and phosphate radicals is used as a photo-thermal catalyst and is uniformly mixed with a waste plastic precursor, nitrogen or argon is introduced into the photo-thermal reactor until an oxygen signal peak cannot be detected in a gas chromatogram, a xenon lamp light source is used for simulating sunlight, and the obtained product is high value-added fuel and an environment repairing material.
Further preferably, the high value-added fuel and environment-repairing material comprises H 2 High added value C1-C7 gas, C8-C30 medium carbon oil, high carbon wax and iron carbon environment repairing material.
Further preferably, the mass ratio of the addition amount of the oxygen acid radical modified zero-valent iron material to the waste plastic to be processed is 5: 1-1: 10.
Further preferably, the photothermal reaction time is 1 to 8 hours.
Preferably, the waste plastics include, but are not limited to, polyethylene, polyvinyl chloride, polystyrene, polypropylene, polyurethane, polyethylene terephthalate.
In the invention, photothermal catalysis can not only trigger traditional photochemical (photocatalytic) reaction by absorbing ultraviolet and visible light, but also utilize residual solar energy including nano-scale local heat generated in the process of compounding infrared photons and carriers by means of photothermal chemistry, and excited state photochemical and non-equilibrium state photothermal effects reduce the reaction energy barrier and increase the conversion rate, thereby optimizing the thermodynamics and kinetics of various challenging catalytic reactions. The method can improve the conversion efficiency of solar energy to chemical energy to the maximum extent, does not need water, and has incomparable advantages of traditional liquid phase photocatalysis in industrial amplification application.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the oxygen-containing acid radical modified zero-valent iron material is used as a catalyst for photo-thermal catalytic conversion of waste plastics, so that high-value-added fuel and an environment repairing material can be simultaneously and efficiently prepared, the conversion rate of a gaseous hydrocarbon product can reach more than 53%, the stability is good, meanwhile, the residual iron-carbon solid can be used as the environment repairing material, organic pollutants and heavy metals in underground water and soil can be efficiently removed, and high efficiency is maintained for a long time;
2. the invention uses oxygen-containing acid radical to modify and treat zero-valent iron, successfully prepares an efficient photothermal conversion waste plastic catalyst, and the catalyst can effectively photothermally convert waste plastic into high value-added fuel and environment restoration material for a long time under the irradiation of solar light;
3. the oxygen-containing acid radical modified on the surface of the zero-valent iron can change the surface pH value of the zero-valent iron without influencing the sunlight response capability of the zero-valent iron, so that the C1-C7 hydrocarbon and the conversion rate and the selectivity in the conversion process of the photothermal waste plastic are improved, and the oxygen-containing acid radical modified zero-valent iron photothermal catalyst with full solar spectrum response capability is prepared by mechanical co-ball milling;
4. the invention skillfully provides a new way for recycling the next generation of waste plastics, which has the advantages of circular economy, environmental protection, controllable carbon emission and large-scale production, the gas product can be used as high value-added fuel, the solid product can be used as a high-efficiency environment-repairing material, and the synchronous combination of waste plastic reclamation, pollution control and carbon emission is realized;
5. the modification of the oxygen-containing acid radicals in the oxygen-containing acid radical modified zero-valent iron photo-thermal catalytic material is a surface substitution strategy, and the oxygen-containing acid radicals are less in consumption, so that the material cost is reduced, and the economic benefit of the material is improved;
6. the invention uses the iron-carbon material after carbon deposition as the environment repairing material, thereby realizing the secondary utilization of the material;
7. the material is environment-friendly, does not cause secondary pollution and has certain cyclicity;
8. the catalyst has the advantages of cheap and easily obtained raw materials, easily realized preparation conditions, no need of complex devices, simple operation, no danger and no need of hiring professional personnel for operation.
Drawings
FIG. 1 is an XRD pattern of ball-milled zero-valent iron and ball-milled oxysalt-modified zero-valent iron synthesized in example 1;
FIG. 2 is an SEM image of the micron-sized ball-milled zero-valent iron and the ball-milled oxysalt-modified zero-valent iron synthesized in example 1;
FIG. 3 is an SEM image of the nanoscale ball-milled zero-valent iron and the ball-milled oxysalt-modified zero-valent iron synthesized in example 1;
FIG. 4 is a TEM image of a synthetic ball-milled zero-valent iron and a ball-milled oxygen-containing acid radical modified zero-valent iron;
FIG. 5 shows the content change of C1-C7 hydrocarbons detected by gas chromatography-mass spectrometry;
FIG. 6 shows the change in the content of gaseous products generated by photothermal conversion of waste plastics by ball milling of zero-valent iron modified with an oxyacid group;
FIG. 7 shows the contents of C1-C7 hydrocarbons in ball-milled zero-valent iron and ball-milled oxygen-containing acid radical-modified zero-valent iron photothermal conversion waste plastics;
FIG. 8 shows the content change of C1-C7 hydrocarbons in the waste plastic by photothermal conversion of ball-milled zero-valent iron and unground zero-valent iron;
FIG. 9 shows the content change of C1-C7 hydrocarbons in the waste plastic by photo-thermal conversion of oxygen-containing acid radical modified zero-valent iron ball-milled in an air atmosphere and oxygen-containing acid radical modified zero-valent iron ball-milled in an inert atmosphere;
FIG. 10 shows the content change of C1-C7 hydrocarbons in ball-milled boric acid/phosphate, carbonate, sulfate and silicate modified zero-valent iron photothermal conversion waste plastics.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples.
Example 1
Preparing ball-milled oxygen-containing acid radical modified zero-valent iron:
placing 5.6g of commercial zero-valent iron powder (with the particle size of 80-150 microns) in an agate ball milling tank, then adding 0.62g of boric acid and 0.73g of sodium phosphate, introducing inert gas into the ball milling tank, carrying out ball milling for 5 hours at the rotating speed of 500 revolutions per minute, and collecting the material after naturally cooling to the room temperature to obtain the oxyacid radical modified zero-valent iron material. According to IPC-OES test, the surface boric acid content is 5.12%, and the surface phosphate radical content is 3.43%.
FIG. 1 is an XRD (X-ray diffraction) diagram of ball-milled zero-valent iron and ball-milled oxygen-containing acid radical modified zero-valent iron; from the XRD pattern, the main component of the synthetic material is zero-valent iron.
FIG. 2 is SEM images of micron-sized ball-milled zero-valent iron and ball-milled oxygen-containing acid radical modified zero-valent iron: as can be seen from the SEM image, the particle size (0.5 to 4 μm) of the ball-milled zero-valent iron modified with the oxyacid group is smaller than that (1 to 10 μm) of the ball-milled zero-valent iron. (the figure a is ball-milling zero-valent iron, and the figure b is ball-milling oxygen-containing acid radical modified zero-valent iron)
FIG. 3 is an SEM image of nanoscale ball-milled zero-valent iron and ball-milled oxygen-containing acid radical-modified zero-valent iron: as seen from the SEM image, the particle size of the ball-milled zero-valent iron modified with the oxoacid group is smaller (80 to 300nm) than that of the ball-milled zero-valent iron (500 to 800 nm). (the figure a is ball-milling zero-valent iron, and the figure b is ball-milling oxygen-containing acid radical modified zero-valent iron)
FIG. 4 is a TEM image of ball-milled zero-valent iron and ball-milled oxygen-containing acid radical modified zero-valent iron; it can be known from fig. 4(a) that the ball-milled zero-valent iron is irregular particles and has no coating layer on the surface, and fig. 4(b) that the ball-milled oxygen-containing acid radical modified zero-valent iron mainly consists of an iron core and a carbon coating layer.
Preparing a contrast material ball-milling zero-valent iron:
placing 5.6g of commercial zero-valent iron powder in an agate ball milling tank, then introducing inert gas, carrying out ball milling for 5 hours at the rotating speed of 500 revolutions per minute, and collecting the ball-milled zero-valent iron after naturally cooling to the room temperature.
Example 2
The realization of preparing high value-added hydrocarbon fuel and environment repairing material by photothermal conversion waste plastic:
waste plastics are mainly commercial low-density polyethylene, which is washed, dried, sliced and crushed to form a precursor with a smaller size. 0.1g of waste plastic sample and 0.5g of catalyst (the zero-valent iron modified by the oxyacid radical obtained in example 1) are uniformly mixed, argon is introduced into a photo-thermal reactor, and the oxygen content in the gas in the reactor is sampled and detected until the oxygen concentration is lower than the detection line. The simulated solar light source was turned on, and waste plastics were photothermally converted under lamp current 22A, and the conversion of waste plastics to gaseous products was tested at different photothermal reaction times. The results of the experiment are shown in FIG. 5: in gas chromatography, the content of carbon dioxide, carbon monoxide and hydrocarbon (C1-C7) is the highest when the photothermal reaction time is 8 hours. FIG. 6 shows the detection of C1-C7 hydrocarbons by GC-MS after 8 hours of photothermal reaction. FIG. 7 shows the content change of C1-C7 hydrocarbons in different photo-thermal reaction times of ball-milled zero-valent iron and ball-milled oxygen-containing acid radical modified zero-valent iron, and the graph shows that the ball-milled oxygen-containing acid radical modified zero-valent iron has higher activity of producing C1-C7 hydrocarbons by converting photo-thermal waste plastics.
Comparative example 1
The non-ball-milled zero-valent iron is subjected to photothermal conversion to waste plastics to prepare high-added-value hydrocarbon fuel and an environment repairing material:
0.1g of waste plastic sample and 0.5g of non-ball-milled zero-valent iron are uniformly mixed, argon is introduced into a photo-thermal reactor, and the oxygen content in the gas in the reactor is sampled and detected until the oxygen concentration is lower than the detection line. The simulated solar light source was turned on, and waste plastics were photothermally converted under lamp current 22A, and the conversion of waste plastics to gaseous products was tested at different photothermal reaction times. The experimental results are shown in fig. 8: compared with ball-milled zero-valent iron, unground zero-valent iron cannot convert waste plastics to produce C1-C7 hydrocarbons through photothermal reaction.
Comparative example 2
Ball-milling zero-valent iron in air atmosphere and inert atmosphere to perform photothermal conversion on waste plastics to prepare high-added-value hydrocarbon fuel and an environment repairing material:
0.1g of waste plastic sample and 0.5g of ball-milled oxyacid radical modified zero-valent iron (samples prepared in air atmosphere and inert atmosphere respectively) are uniformly mixed, argon is introduced into a photo-thermal reactor, and the oxygen content in the gas in the reactor is sampled and detected until the oxygen concentration is lower than the detection line. The simulated solar light source was turned on, and waste plastics were photothermally converted under lamp current 22A, and the conversion of waste plastics to gaseous products was tested at different photothermal reaction times. The results of the experiment are shown in fig. 9: compared with the ball milling of the zero-valent iron modified by the oxyacid radical in the inert atmosphere, the ball milling of the zero-valent iron in the air atmosphere cannot convert waste plastics through photothermal reaction to generate C1-C7 hydrocarbon.
Comparative example 3
Other oxygen-containing acid radical modified ball-milling zero-valent iron photothermal conversion waste plastics are used for preparing high-added-value hydrocarbon fuel and environment restoration materials:
0.1g of waste plastic sample and 0.5g of ball-milled zero-valent iron (carbonate, sulfate and silicate respectively) modified by oxyacid radicals are uniformly mixed, argon is introduced into a photo-thermal reactor, and the oxygen content in the gas in the reactor is sampled and detected until the oxygen concentration is lower than that of a detection line. The simulated solar light source was turned on, and waste plastics were photothermally converted under lamp current 22A, and the conversion of waste plastics to gaseous products was tested at different photothermal reaction times. The experimental results are shown in fig. 10: compared with boric acid and phosphate modified ball-milled zero-valent iron, other ball-milled zero-valent iron modified by the oxygen-containing acid radicals (carbonate, sulfate and silicate) cannot be converted into waste plastics through photothermal reaction to generate C1-C7 hydrocarbon.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (10)
1. A method for photothermal conversion of waste plastics into high value-added fuel and environment restoration materials by using zero-valent iron is characterized in that an oxyacid radical modified zero-valent iron material is used as a catalyst for photothermal conversion of the waste plastics, the oxyacid radical modified zero-valent iron material has a micro-scale and/or nano-scale irregular granular micro-morphology structure, and surface species comprise boric acid and phosphate radicals.
2. The method for photothermal conversion of waste plastics into high value-added fuels and environmental remediation materials by using zero-valent iron according to claim 1, wherein the boric acid content of the surface of the oxygen-containing acid radical modified zero-valent iron material is 0.05% to 6.18% by mass.
3. The method for photothermal conversion of waste plastic into high value-added fuel and environmental remediation material using zero-valent iron as claimed in claim 1, wherein the phosphate mass content of the surface of the oxygen-containing acid radical modified zero-valent iron material is 0.01% -3.53%.
4. The method for photothermal conversion of waste plastic into high value-added fuel and environmental remediation material using zero-valent iron as claimed in claim 1, wherein the micron-sized particles are 0.5-10 μm in diameter, and the nanometer-sized particles are 80-800 nm in diameter.
5. The method for photothermal conversion of waste plastics into high value-added fuels and environmental remediation materials by using zero-valent iron according to claim 1, wherein the method for preparing the oxyacid group-modified zero-valent iron material comprises the following steps:
1) mixing the precursor containing the oxygen acid radical with zero-valent iron to obtain solid powder;
2) and mechanically ball-milling the solid powder in an inert atmosphere, and collecting the obtained product after naturally cooling to room temperature to obtain the oxygen-containing acid radical modified zero-valent iron material.
6. The method for photothermal conversion of waste plastics into high value-added fuels and environmental remediation materials using zero-valent iron according to claim 5, wherein the precursor containing oxygen acid radicals in step 1) is boric acid and phosphate.
7. The method for photothermal conversion of waste plastics into high value-added fuels and environment restoration materials according to claim 5, wherein the mechanical ball milling speed in step 2) is 100-500 rpm, and the ball milling time is 1-6 hours.
8. The method for photothermal conversion of waste plastics into high value-added fuel and environmental remediation material by using zero-valent iron according to claim 1, wherein the method comprises the following steps: the method comprises the steps of taking an oxyacid radical modified zero-valent iron material as a photo-thermal catalyst, uniformly mixing the oxyacid radical modified zero-valent iron material with waste plastics, introducing inert gas into a photo-thermal reactor, simulating sunlight by using a xenon lamp light source, and obtaining a product which is a high value-added fuel and an environment repairing material.
9. The method for photothermal conversion of waste plastics into high value-added fuel and environmental remediation material by using zero-valent iron according to claim 8, wherein the mass ratio of the addition amount of the oxygen-containing acid radical modified zero-valent iron material to the waste plastics to be processed is 5: 1-1: 10.
10. The method for photothermal conversion of waste plastics into high value-added fuels and environmental remediation materials by using zero-valent iron according to claim 8, wherein the photothermal reaction time is 1-8 hours.
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| US20140004232A1 (en) * | 2010-12-30 | 2014-01-02 | Uniwersytet Ekonomiczny W Poznaniu | Nanoiron-based oxygen scavengers |
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| US20140004232A1 (en) * | 2010-12-30 | 2014-01-02 | Uniwersytet Ekonomiczny W Poznaniu | Nanoiron-based oxygen scavengers |
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| CN110606538A (en) * | 2019-07-30 | 2019-12-24 | 华中师范大学 | Method for removing pollutants based on efficient reduction of borated zero-valent iron |
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