CN115725318A - Method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on decommissioned polyolefin with two-dimensional nanosheets - Google Patents
Method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on decommissioned polyolefin with two-dimensional nanosheets Download PDFInfo
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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
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Abstract
The invention discloses a method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on decommissioned polyolefin by using two-dimensional nanosheets, which comprises the following steps: the catalytic material is mainly a two-dimensional-high dispersion-low loading noble metal-metal oxide composite nanosheet catalyst, the noble metal in the catalyst is highly dispersed on the surface of the two-dimensional nanosheet layer carrier, and the efficiency of the noble metal is fully exerted compared with other metal loaded catalysts; adding the nanosheet catalyst and the retired polyolefin into a reaction kettle, introducing nitrogen, removing oxygen, hydrogenating, heating, performing catalytic hydrogenolysis, collecting an oil product, and finishing the orientation of the polyolefin chainConverting and breaking; the temperature required by the complete catalytic hydrogenolysis of the polyolefin can be lower than 200 ℃, the yield of light oil can reach more than 80 percent, and the conversion frequency can reach 1456h ‑1 . The invention effectively solves the problems of complex process, poor economic benefit, large environmental pollution and the like in the traditional production process in the retired polyolefin treatment, and realizes the conversion and utilization of the retired polyolefin with high activity, high selectivity and high stability.
Description
Technical Field
The invention belongs to the field of high-value utilization of retired polyolefin, and particularly relates to a method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on retired polyolefin by using two-dimensional nanosheets.
Background
With the progress of polymer synthesis technology, plastics have been advanced into various fields of production and life of people, and the plastics are widely applied to electric insulators, pipelines, plastic packages and films due to the characteristics of light weight, easiness in processing, corrosion resistance, low cost and the like. However, plastics are slow to degrade naturally due to their chemical stability, causing an increasingly serious problem of "white contamination". Over the past decades, the production of globally synthesized petroleum-based plastics has increased dramatically, approaching 3.6 million tons in 2018, with the production expected to double again within the next 20 years. However, currently about 70% of plastics are not properly disposed of, causing serious soil hardening, river and ocean environmental pollution, and atmospheric pollution problems.
The existing methods for treating waste plastics mainly comprise landfill, incineration, thermal cracking, catalytic cracking and the like. The natural degradation rate of waste plastics such as Polyethylene (PE) mulching films is extremely low, at least 200 years are needed for complete natural degradation, a large amount of land resources are occupied for a long time, and toxic and harmful substances contained in the aging process of the waste plastics are leached and diffused to the land, so that the landfill method is not suitable for the treatment of the waste plastics which are difficult to naturally degrade. Incineration of waste plastics for large-scale volume reduction and energy recoveryEffective means, however, the waste plastic incineration is accompanied with the generation of toxic organic gases such as polycyclic aromatic hydrocarbon, dioxin, furan and the like; plastics (such as PVC, PU and the like) containing chlorine and nitrogen and additives (such as bromine-containing flame retardant) can release NO during incineration x Inorganic pollutants such as HCl, HBr and HCN are easy to cause secondary pollution to the environment. In addition, because of the obvious difference of the heat values of various plastics, the instability of the raw material composition can also cause the instability of combustion. The waste plastics are converted by high temperature and high pressure in the thermal cracking resource utilization of the waste plastics, the thermal cracking energy consumption is high, the product value is low, and the quality of the waste plastics fluctuates obviously under the influence of the purity, the variety and the like of raw materials. The catalytic cracking adopts a catalyst to regulate and control the reaction process and the product distribution, and can realize the controllable breakage of polymer molecular chains. Wherein, the catalytic hydrogenolysis can reduce the temperature required by the reaction and accelerate the breaking of long-chain molecules; the volume of the reactor is reduced, and the energy consumption and the operation and maintenance cost are reduced; the enrichment of target products can be realized, the viscosity of the pyrolysis oil is reduced, the molecular weight distribution of the products is optimized, and the product value is improved.
At present, most of catalysts for catalytic hydrogenolysis of retired polyolefin are metal-loaded catalysts of various zeolite molecular sieves such as HZSM-5 and ZSM-5, and the catalytic hydrogenolysis reaction temperature is high, the energy consumption is high, coking is easy, and the efficiency is low. The two-dimensional metal oxide material has many exposed active sites, rich surface defects and controllable quantity and property, has strong interaction with noble metal compared with zeolite, is beneficial to hydrogen atom adsorption, has strong stability, and is widely concerned as a noble metal catalyst carrier. The metal sites are usually composed of noble metals such as platinum, ruthenium and alloys thereof, the noble metals have a hydrogen overflow phenomenon in the catalytic hydrogenolysis process, compared with common metals, the hydrogen overflow phenomenon can greatly reduce the carbon bond breaking activation energy, prepare the ultrahigh-efficiency and stable two-dimensional catalytic hydrogenolysis catalyst, and greatly improve the catalytic hydrogenolysis efficiency of the decommissioned polyolefin.
Disclosure of Invention
The invention aims to provide a method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on retired polyolefin by using two-dimensional nanosheets, aiming at the problems of serious environmental pollution, harsh reaction conditions, low efficiency, poor product quality, need of complicated procedures for separation and purification and the like in the high-value conversion of the existing retired polyolefin.
The purpose of the invention is realized by the following technical scheme: a method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on decommissioned polyolefin by using two-dimensional nanosheets is characterized by comprising the following steps of:
preparing a two-dimensional-high-dispersion-low-load precious metal-metal oxide composite nanosheet catalyst by adopting a catalyst preparation method, and mixing the prepared catalyst and retired polyolefin according to a mass ratio of 1; and placing the mixed solid in a reaction kettle, carrying out catalytic hydrogenolysis reaction under the conditions that the reaction temperature is 180-300 ℃, the reaction hydrogen pressure is 0.01-6 MPa and the reaction time is 0.1-72 h, so as to directionally fracture the retired polyolefin chain to obtain a gaseous product, a liquid product and a solid product, and extracting and separating the liquid product by using an extraction solvent to obtain the light oil.
Optionally, the catalyst preparation method comprises a space confinement method, an impregnation method, a coprecipitation method, an atomic deposition method and a hydrothermal method.
Optionally, the two-dimensional-high dispersion-low loading noble metal-metal oxide composite nanosheet catalyst comprises Pt/WO 3 、Pt/CeO 2 、Ru/WO 3 、Rh/WO 3 、Pt/Nb 2 O 5 、Ru/Nb 2 O 5 、Ru/CeO 2 、Pt/Al 2 O 3 、Pt/ZrO 2 And Pt/ZrWO x (ii) a The content of the low-load noble metal is 0.001-1 wt.%.
Optionally, the thickness of the composite nano-sheet is 0.6-2nm, and the diameter of the composite nano-sheet is 0.1-10 μm.
Optionally, the two-dimensional-high dispersion-low loading amount precious metal-metal oxide composite nanosheet catalyst and the decommissioned polyolefin are mixed by mechanical stirring or screw extrusion.
Optionally, the decommissioned polyolefin is mixed by one or more of low density polyethylene, high density polyethylene, polypropylene and polystyrene according to any proportion.
Alternatively, the extraction solvent comprises n-hexane, toluene, xylene, mesitylene, dichloromethane, and carbon disulfide.
Optionally, the light oil comprises gasoline, diesel.
Optionally, the method is characterized in that the solid product is calcined and reduced under the conditions that the reduction temperature is 200-500 ℃, the heating rate is 1-10 ℃/min, and the reduction time is 0.5-6 h, so as to separate the two-dimensional-high dispersion-low loading amount precious metal-metal oxide composite nanosheet catalyst from the retired polyolefin residue, and thus, the cycle stability test of the two-dimensional-high dispersion-low loading amount precious metal-metal oxide composite nanosheet catalyst is realized.
Optionally, the number of the cycle stability tests is greater than or equal to 5.
The method has the advantages that the precious metal is fully, effectively and highly dispersed on the surface of the carrier, the catalytic activity efficiency of the precious metal can be fully exerted, the precious metal has extremely high activity under extremely low loading capacity, the cracking temperature can be effectively reduced to be below 200 ℃, and the reaction time is shortened to be 3 hours. The high-dispersion noble metal supported catalyst is used for catalyzing hydrogenolysis of decommissioned polyolefin, so that the polymer chain is directionally converted and broken in a one-step method, high-yield light oil is obtained, and high-selectivity conversion and utilization of the decommissioned polyolefin are realized. The feasibility of catalyzing the hydrogenolysis reaction process of High Density Polyethylene (HDPE) was demonstrated. The invention effectively solves the problems of complex process, poor economic benefit, large environmental pollution and the like in the traditional production process in the retired polyolefin treatment, is simple and efficient, is easy for industrial production, and realizes the cyclic comprehensive utilization of the retired polyolefin.
Drawings
FIG. 1 is a process flow diagram for preparing light oil by catalytic hydrogenolysis conversion of retired polyolefin;
FIG. 2 is a carbon number distribution diagram of a catalytic hydrogenolysis conversion product of retired polyolefin;
FIG. 3 is a graph showing the yield of light oil produced by catalytic hydrogenolysis conversion of a decommissioned polyolefin;
figure 4 is the cyclic regeneration stability of a decommissioned polyolefin catalytic hydrogenolysis catalyst.
In the figure: a high-temperature high-pressure kettle type reactor 1, a solvent recovery tower 2 and a rectifying tower 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for preparing light oil by catalytic hydrogenolysis conversion of retired polyolefin, which is further detailed in the following for making the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Firstly, a catalyst preparation method is adopted to prepare the two-dimensional-high-dispersion-low-load precious metal-metal oxide composite nanosheet catalyst, including but not limited to: pt/WO 3 、Pt/CeO 2 、Ru/WO 3 、Rh/WO 3 、Pt/Nb 2 O 5 、Ru/Nb 2 O 5 、Ru/CeO 2 、Pt/Al 2 O 3 、Pt/ZrO 2 And Pt/ZrWO x . Wherein the thickness of the composite nano-sheet is 0.6-2nm, and the diameter is 0.1-10 μm.
Specifically, the high-dispersion noble metal supported catalyst can be prepared by a space confinement method, an impregnation method, a coprecipitation method, an atomic deposition method, a hydrothermal method or the like. Wherein the noble metal loading is from 0.001wt% to 1wt%.
In this embodiment, the decommissioned polyolefin comprises at least one of Low Density Polyethylene (LDPE), high Density Polyethylene (HDPE), polypropylene (PP), and Polystyrene (PS). It is readily understood that the retired polyolefin may be one kind or a mixture of two or more kinds.
In the embodiment, the prepared two-dimensional-high-dispersion-low-load-capacity precious metal-metal oxide composite nanosheet catalyst and the retired polyolefin are mixed according to the ratio of 1; then placing the mixed solid in a reaction kettle, and carrying out catalytic hydrogenolysis reaction on the mixed solid under the conditions that the reaction temperature is 180-300 ℃, the reaction hydrogen pressure is 0.01-6 MPa, and the reaction time is 0.1-72 h, so that the retired polyolefin chain can be directionally fractured, and a gaseous product, a liquid product or a solid product can be obtained. Wherein the gaseous product comprises C1-C4 low-carbon alkane gas, the liquid product comprises C5-C20 normal or isoparaffin, the solid product comprises unreacted retired polyolefin residue and a two-dimensional-high dispersion-low load precious metal-metal oxide composite nanosheet catalyst, the content of the C1-C4 low-carbon alkane gas is less than 17wt.%, the content of the C5-C20 normal or isoparaffin is 70wt.% to 90wt.%, and the content of the retired polyolefin residue and the two-dimensional-high dispersion-low load precious metal-metal oxide composite nanosheet catalyst is less than 10wt.%.
Wherein, the catalytic hydrogenolysis reaction is carried out by adopting a two-dimensional-high dispersion-low loading amount noble metal-metal oxide composite nanosheet catalyst, so that the nearly complete hydrogenolysis of the retired polyolefin is realized, the conversion frequency is high and can reach 1456h -1 。
In this embodiment, the liquid product generated after catalytic hydrogenolysis is extracted and separated by an extraction solvent, so that light oil can be obtained. Wherein the extraction solvent comprises n-hexane, toluene, xylene, mesitylene, dichloromethane and carbon disulfide. The yield of the light oil is high, and the yield of the obtained light oil is not lower than 80%.
It should be understood that light oils include, but are not limited to: gasoline, diesel oil, aviation kerosene.
In addition, the solid product generated by catalytic hydrogenolysis contains the two-dimensional-high dispersion-low loading amount precious metal-metal oxide composite nanosheet catalyst, and the catalyst can be separated from the retired polyolefin residue, so that the two-dimensional-high dispersion-low loading amount precious metal-metal oxide composite nanosheet catalyst can be recycled. Calcining and reducing the solid product under the conditions of reduction temperature of 200-500 ℃, heating rate of 1-10 ℃/min and reduction time of 0.5-6 h, and separating the two-dimensional-high dispersion-low load precious metal-metal oxide composite nanosheet catalyst from the retired polyolefin residue to realize the circulation stability test of the two-dimensional-high dispersion-low load precious metal-metal oxide composite nanosheet catalyst. The number of times of the cyclic stability is not less than 5, and the evaluation criterion is the number of times of cyclic regeneration with the performance reduction of less than 5%, so that the cyclic stability is good.
The method for preparing light oil by catalytic hydrogenolysis of retired polyolefin by two-dimensional nanosheets in the present invention will be described in detail below with reference to examples, and the objects and effects of the present invention will become more apparent.
Example 1
Pt/WO (platinum/tungsten oxide) prepared by adopting space confinement method 3 . 20.4g of Mg (NO) 3 ) 2 ·6H 2 O、15.2g Al(NO 3 ) 3 ·9H 2 O and 12.8g NaOH were dissolved in 600mL of deionized water and purged with nitrogen and the pH was controlled at 10.0. Stirring at room temperature for 30min, and aging at 80 deg.C under nitrogen protection for 12 hr to obtain nitrate ion intercalation metal hydroxide (LDHs). Adding 2.0g of LDHs and 2.0g of ammonium metatungstate into 40ml of deionized water, and stirring for 24 hours at 40 ℃ to obtain the metatungstate anion intercalation LDHs compound. Calcining 2g of metatungstate anion intercalation LDHs compound at 550 ℃ for 2h to obtain the tungsten trioxide mixed metal oxide. Adding 1g of tungsten trioxide mixed metal oxide into 100mL of 0.5mol/L hydrochloric acid aqueous solution, and freeze-drying for 10h to obtain WO 3 ·H 2 O two-dimensional nanosheet. 2g of WO 3 ·H 2 Dispersing an O two-dimensional nanosheet in 100mL of deionized water, dropwise adding 20mL of 2g/L chloroplatinic acid aqueous solution under the stirring condition, filtering and drying to obtain the chloroplatinic acid-adsorbed WO 3 ·H 2 O two-dimensional nanosheets; placing the nanosheets in 5vol% 2 Calcining for 2h at 350 ℃ in a/Ar atmosphere at the heating rate of 10 ℃/min to obtain the Pt supported two-dimensional tungsten oxide nanosheet catalyst, wherein the Pt supporting amount is 0.19wt%.
As shown in FIG. 1, 0.19% Pt/WO of the preparation in the reaction kettle 3 And (3) carrying out a catalytic conversion activity test on the retired high-density polyethylene. Accurately weighing 0.1g of catalyst and 1.0g of retired high density polyethylene in a reaction kettle, introducing nitrogen to remove oxygen for 1h, and reacting for 3h at 250 ℃ under the hydrogen pressure of 3.0 MPa. Cooling to room temperature to obtainGaseous, liquid or solid products. Wherein the gaseous product comprises C1-C4 low-carbon alkane gas, the liquid product comprises C5-C20 normal or isoparaffin, and the solid product comprises unreacted plastic residue and high-dispersion precious metal supported catalyst. And analyzing and quantifying the gas by using a gas chromatography-mass spectrometer. After the air is exhausted, n-hexane is added into the reaction kettle to extract liquid products and simultaneously separate the catalyst, and the liquid is analyzed and quantified by a gas chromatography-mass spectrometer. The conversion rate of the obtained retired high-density polyethylene is up to more than 99 percent, wherein the yield of light oil is 87 percent (shown in figures 2 and 3), and the conversion frequency is 1456h -1 . Calcining and reducing the solid product under the conditions of the reduction temperature of 300 ℃, the heating rate of 5 ℃/min and the reduction time of 1h, and separating the high-dispersion noble metal supported catalyst from the plastic residues. The performance of the recovered catalyst was reduced by less than 5% after 5 cycles, as shown in fig. 4.
Example 2
Preparation of Pt/CeO by coprecipitation method 2 . 2.17g of Ce (NO) was taken 3 ) 3 ·6H 2 Dissolving O in 20mL of deionized water, adding 60mL of 8M NaOH solution under stirring, putting the mixture into a stainless steel high-temperature reaction kettle, and reacting at 100 ℃ for 24 hours to obtain white precipitate. Washing the precipitate with deionized water, calcining the white precipitate at 400 ℃ for 4h in air atmosphere to obtain two-dimensional CeO 2 Nanosheets. NaOH (0.22g, 5.5 mmol) was dissolved in 20mL of Ethylene Glycol (EG) to obtain 0.02g of H 2 PtCl 6 ·6H 2 Dissolving O in 20mL of ethylene glycol, mixing the two solutions together, stirring at room temperature for 1h, and heating at 90 ℃ for 2h under the protection of nitrogen to obtain a colloidal solution. 60mL of 2M HCl solution is added to obtain platinum particle colloidal solution, the platinum particle colloidal solution is centrifuged and re-dispersed in 20mL of ethanol solution to obtain 1mg/mL of platinum particle dispersion for later use, and 4mg of polyvinylpyrrolidone (PVP) is added as a stabilizer. 0.5g of two-dimensional CeO 2 Dispersing the nanosheets in 20mL of ethanol, adding 20mL of platinum particle dispersion, stirring at room temperature for 12h, drying at 60 ℃ under vacuum for 12h, placing the catalyst at 5vol% 2 Calcining for 2h at 350 ℃ in an Ar atmosphere at the heating rate of 10 ℃/min to obtain Pt loaded on two-dimensional CeO 2 The nano-sheet catalyst has a Pt loading of 0.50wt%.
0.50% of Pt/CeO prepared in a reaction vessel 2 The catalyst is subjected to a catalytic conversion activity test of the retired low density polyethylene. Accurately weighing 0.05g of catalyst and 1.0g of retired low-density polyethylene in a reaction kettle, introducing nitrogen to remove oxygen for 1h, and reacting for 12h at 220 ℃ and under the hydrogen pressure of 4.0 MPa. After cooling to room temperature, a gaseous, liquid or solid product is obtained. Wherein the gaseous product comprises C1-C4 low-carbon alkane gas, the liquid product comprises C5-C20 normal or isoparaffin, and the solid product comprises unreacted plastic residue and a high-dispersion noble metal supported catalyst. And analyzing and quantifying the gas by using a gas chromatography-mass spectrometer. After the air is exhausted, dichloromethane is added into the reaction kettle to extract liquid products and simultaneously separate the catalyst, and the liquid is analyzed and quantified by a gas chromatography-mass spectrometer. The conversion rate of the obtained retired low-density polyethylene reaches more than 90 percent, wherein the yield of light oil is 80 percent, and the conversion frequency is 237h -1 . And calcining and reducing the solid product under the conditions of the reduction temperature of 250 ℃, the heating rate of 5 ℃/min and the reduction time of 1h, and separating the high-dispersion noble metal supported catalyst from the plastic residues. The performance of the recovered catalyst is reduced by less than 5 percent after 5 times of recycling.
Example 3
Preparation of Pt/ZrWO by adopting impregnation method x .1g of ZrOCl is taken 2 Dissolving in 20mL deionized water, adding 1M ammonia water dropwise to adjust the pH of the solution to 11, and precipitating at room temperature for 12h to obtain Zr (OH) 4 And (4) precipitating. The precipitate was washed several times with deionized water, filtered, separated and dried under vacuum at 60 ℃ for 12h. Preparing 10mL of 10mg/mL ammonium metatungstate hydrate solution, and adding Zr (OH) 4 Dispersing the powder into ammonium metatungstate aqueous solution, stirring at room temperature for 12h, filtering and separating the mixture, vacuum drying at 60 deg.C for 12h, calcining at 800 deg.C in air atmosphere for 3h to obtain two-dimensional ZrWO x A nanosheet. Weighing 1g of two-dimensional ZrWO x The nano-sheets are dispersed into 20mL of 2g/L H 2 PtCl 6 ·6H 2 Stirring in an aqueous O solution at room temperature for 12h, separating the mixture by filtration, vacuum drying at 60 ℃ for 12h, at 350 ℃ 5vol% 2 Calcination in Ar atmosphereObtaining Pt loaded on two-dimensional Pt/ZrWO within 2h x The nano-sheet catalyst has a Pt loading of 1.0wt%.
1.0% of the preparation in the reaction kettle x The catalyst is used for carrying out the catalytic conversion activity test of the retired polystyrene. Accurately weighing 0.02g of catalyst and 1.0g of retired polystyrene in a reaction kettle, introducing nitrogen to remove oxygen for 1h, and reacting for 48h at 280 ℃ and under the hydrogen pressure of 2.0 MPa. After cooling to room temperature, a gaseous, liquid or solid product is obtained. Wherein the gaseous product comprises C1-C4 low-carbon alkane gas, the liquid product comprises C5-C20 normal or isoparaffin, and the solid product comprises unreacted plastic residue and a high-dispersion noble metal supported catalyst. And analyzing and quantifying the gas by using a gas chromatography-mass spectrometer. After the air is exhausted, toluene is added into the reaction kettle to extract liquid products and simultaneously separate the catalyst, and the liquid is analyzed and quantified by a gas chromatography-mass spectrometer. The conversion rate of the obtained retired polystyrene is up to more than 87 percent, wherein the yield of the light oil is 81 percent, and the conversion frequency is 73 hours -1 . Calcining and reducing the solid product under the conditions of the reduction temperature of 300 ℃, the heating rate of 10 ℃/min and the reduction time of 2h, and separating the high-dispersion noble metal supported catalyst from the plastic residues. The performance of the recovered catalyst is reduced by less than 5 percent after 8 times of recycling.
Example 4
Preparation of Rh/Nb by atomic deposition method 2 O 5 . Decomposition of [ Nb (OiPr) on a gold sputtered alumina substrate at 950 ℃ in a tube furnace 5 ] 2 Preparation of two-dimensional Nb from precursor 2 O 5 Nanosheets. 500mL of [ (NH) 200mg/L 4 ) 3 Rh] 6+ Adding 1M ammonia water dropwise into the aqueous solution to adjust the pH of the solution to about 10, and adding Nb 2 O 5 Stirring at room temperature for 12h, filtering to separate out the solid after completion, vacuum drying at 60 deg.C for 12h, at 400 deg.C, 5vol% 2 Calcining for 2h in Ar atmosphere to obtain Rh loaded on two-dimensional Nb 2 O 5 Nanosheet catalyst, rh loading 0.01wt%.
0.01% Rh/Nb for the preparation in a reaction vessel 2 O 5 Catalytic conversion activity test of catalyst for retired polypropyleneAnd (6) testing. Accurately weighing 0.1g of catalyst and 1.0g of retired polypropylene in a reaction kettle, introducing nitrogen to remove oxygen for 1h, and reacting for 72h at 200 ℃ and under the hydrogen pressure of 2.0 MPa. After cooling to room temperature, a gaseous, liquid or solid product is obtained. Wherein the gaseous product comprises C1-C4 low-carbon alkane gas, the liquid product comprises C5-C20 normal or isoparaffin, and the solid product comprises unreacted plastic residue and high-dispersion precious metal supported catalyst. And analyzing and quantifying the gas by using a gas chromatography-mass spectrometer. After the air is exhausted, the mesitylene is added into the reaction kettle to extract the liquid product and simultaneously separate the catalyst, and the liquid is analyzed and quantified by a gas chromatography-mass spectrometer. The conversion rate of the obtained retired polypropylene is up to more than 95 percent, wherein the yield of the light oil is 90 percent, and the conversion frequency is 1187 hours -1 . And calcining and reducing the solid product under the conditions that the reduction temperature is 300 ℃, the heating rate is 3 ℃/min and the reduction time is 2h, and separating the high-dispersion noble metal supported catalyst from the plastic residues. The performance of the recovered catalyst is reduced by less than 5 percent after 10 times of recycling.
Example 5
Preparation of Ru/CeO by hydrothermal method 2 . 2.17g of Ce (NO) was taken 3 ) 3 ·6H 2 O was dissolved in 20mL of deionized water, and 60mL of a 8M aqueous solution of terephthalic acid was added with stirring. And transferring the mixture into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into a stainless steel high-temperature reaction kettle, and carrying out hydrothermal reaction at 100 ℃ for 24 hours to obtain white powder. Washing a sample by deionized water, and calcining white powder at 400 ℃ for 4h in an air atmosphere to obtain two-dimensional CeO 2 A nanosheet. 100mg of RuCl 3 Dissolving the mixture in 20mL of deionized water, and dissolving the two-dimensional CeO 2 Dispersing the nanosheets into an aqueous Ru solution, stirring at room temperature for 12h, filtering to separate a solid sample, drying at 60 ℃ under vacuum for 12h, subjecting the sample to 350 ℃ at 5vol% 2 Calcining for 2h in the Ar atmosphere at the heating rate of 10 ℃/min, and naturally cooling to obtain Ru-loaded two-dimensional CeO 2 The catalyst on the nano-chip has a Ru loading of 0.60wt%.
0.60% Ru/CeO of the preparation in a reaction vessel 2 And (3) carrying out a catalytic conversion activity test on the retired high-density polyethylene. Accurately weighing 0.01g of catalyst1.0g of retired high-density polyethylene is put into a reaction kettle, nitrogen is introduced to remove oxygen for 1h, and the reaction is carried out for 24h at 280 ℃ and under the hydrogen pressure of 6.0 MPa. After cooling to room temperature, a gaseous product, a liquid product or a solid product is obtained. Wherein the gaseous product comprises C1-C4 low-carbon alkane gas, the liquid product comprises C5-C20 normal or isoparaffin, and the solid product comprises unreacted plastic residue and a high-dispersion noble metal supported catalyst. And analyzing and quantifying the gas by using a gas chromatography-mass spectrometer. After the air is exhausted, xylene is added into the reaction kettle to extract liquid products and simultaneously separate the catalyst, and the liquid is analyzed and quantified by a gas chromatography-mass spectrometer. The conversion rate of the obtained retired high-density polyethylene reaches more than 98 percent, wherein the yield of the light oil is 83 percent, and the conversion frequency is 564h -1 . Calcining and reducing the solid product under the conditions of the reduction temperature of 400 ℃, the heating rate of 3 ℃/min and the reduction time of 1h, and separating the high-dispersion noble metal supported catalyst from the plastic residues. The performance of the recovered catalyst is reduced by less than 5 percent after 5 times of recycling.
In summary, the method for preparing the light oil by catalytic hydrogenolysis conversion of the decommissioned polyolefin firstly provides that the decommissioned polyolefin is catalyzed to carry out hydrogenolysis reaction under the conditions of certain pressure and relative low temperature below 300 ℃ by applying the two-dimensional, high-dispersion and low-load amount of the noble metal-metal oxide composite nanosheets. The method is a novel method for catalytic conversion and high-value recycling of retired polyolefin, can convert the retired polyolefin into light oil with high added value, and is simple and effective.
It will be understood that the invention is not limited to the examples described above, but that modifications and variations can be effected by a person skilled in the art in light of the above description, all within the scope of the invention as defined by the appended claims. The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on decommissioned polyolefin by using two-dimensional nanosheets is characterized by comprising the following steps of:
preparing a two-dimensional-high-dispersion-low-load precious metal-metal oxide composite nanosheet catalyst by adopting a catalyst preparation method, and mixing the prepared catalyst and the retired polyolefin according to a mass ratio of 1; and placing the mixed solid in a reaction kettle, carrying out catalytic hydrogenolysis reaction under the conditions that the reaction temperature is 180-300 ℃, the reaction hydrogen pressure is 0.01-6 MPa and the reaction time is 0.1-72 h, so as to directionally fracture the retired polyolefin chain to obtain a gaseous product, a liquid product and a solid product, and extracting and separating the liquid product by using an extraction solvent to obtain the light oil.
2. The method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on decommissioned polyolefins with two-dimensional nanosheets as claimed in claim 1, wherein the catalyst preparation method comprises a space-limited method, an impregnation method, a coprecipitation method, an atomic deposition method and a hydrothermal method.
3. The method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on decommissioned polyolefin with two-dimensional nanosheets according to claim 1, wherein the two-dimensional-high dispersion-low loading amount precious metal-metal oxide composite nanosheet catalyst comprises Pt/WO 3 、Pt/CeO 2 、Ru/WO 3 、Rh/WO 3 、Pt/Nb 2 O 5 、Ru/Nb 2 O 5 、Ru/CeO 2 、Pt/Al 2 O 3 、Pt/ZrO 2 And Pt/ZrWO x (ii) a The content of the low-load noble metal is 0.001-1 wt.%.
4. The method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on the decommissioned polyolefin by using the two-dimensional nano sheets as claimed in claim 1, wherein the thickness of the composite nano sheets is 0.6-2nm, and the diameter of the composite nano sheets is 0.1-10 μm.
5. The method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on the decommissioned polyolefin by using the two-dimensional nanosheets as claimed in claim 1, wherein the mixing mode of the two-dimensional-high-dispersion-low-loading-amount precious metal-metal oxide composite nanosheet catalyst and the decommissioned polyolefin is mechanical stirring mixing or screw extrusion mixing.
6. The method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on the decommissioned polyolefin by using the two-dimensional nanosheets of claim 1, wherein the decommissioned polyolefin is prepared by mixing one or more of low-density polyethylene, high-density polyethylene, polypropylene and polystyrene according to any proportion.
7. The method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on retired polyolefin by using two-dimensional nanosheets as claimed in claim 1, wherein the extraction solvent comprises n-hexane, toluene, xylene, mesitylene, dichloromethane, and carbon disulfide.
8. The method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on the ex-service polyolefin with the two-dimensional nano-sheets according to claim 1, wherein the light oil comprises gasoline and diesel oil.
9. The method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on the decommissioned polyolefin by using the two-dimensional nanosheets as claimed in claim 1, wherein the solid product is calcined and reduced under the conditions of a reduction temperature of 200-500 ℃, a temperature rise rate of 1-10 ℃/min, and a reduction time of 0.5-6 h, so as to separate the two-dimensional-high-dispersion-low-loading-amount precious metal-metal oxide composite nanosheet catalyst from the decommissioned polyolefin residue, so as to realize the cycle stability test of the two-dimensional-high-dispersion-low-loading-amount precious metal-metal oxide composite nanosheet catalyst.
10. The method for preparing light oil by carrying out low-temperature catalytic hydrogenolysis on the two-dimensional nanosheet of the decommissioned polyolefin according to claim 9, wherein the number of the cycling stability tests is 5 or more.
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