Method for preparing fuel oil from waste chlorine-containing high polymer material

Abstract

The invention belongs to the technical field of waste plastic chemical recovery and resource utilization, and particularly relates to a method for preparing fuel oil by adopting a waste chlorine-containing high polymer material. Comprising the following steps: S1, pretreating the waste chlorine-containing high polymer material and polystyrene; s2, adding a catalyst and uniformly mixing; s3, carrying out synergistic dechlorination and chain scission degradation reaction under the action of a catalyst; and S4, after the reaction is finished, cooling and separating the reaction system. According to the method, a waste chlorine-containing mixed plastic and rubber system which is complex in component and difficult to sort can be treated, and synergistic dechlorination and degradation conversion are achieved; compared with a traditional high-temperature pyrolysis route, conversion can be achieved at the low temperature or in an ultrasonic / mechanochemical mode, and reduction of energy consumption and side reactions is facilitated; through dechlorination and conversion, adverse effects of chlorine-containing components on equipment corrosion and product quality can be reduced, and the method has good engineering application potential.

Description

Technical Field

[0001] This invention relates to the field of chemical recycling and resource utilization of waste plastics, specifically a method for preparing fuel oil using waste chlorine-containing polymer materials. Background Technology

[0002] Liquid hydrocarbon fuels have long held an important position in transportation, engineering machinery, and industry due to their high energy density and ease of storage, transportation, and use. Currently, liquid fuels mainly rely on petroleum resources, making them highly susceptible to fluctuations in resource conditions and costs. Meanwhile, industrial production and daily consumption generate vast quantities of waste plastics and rubber materials. These materials, rich in hydrocarbon structures, have potential value as fuel feedstocks. If waste polymer materials can be converted into liquid fuels through appropriate conversion methods, it will not only help expand fuel sources but also realize the resource utilization of solid waste.

[0003] Among various waste polymer materials, chlorinated plastics and rubbers face significant technical challenges in fuel utilization due to their unique chemical composition and thermal reactivity. These materials, including but not limited to polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and chloroprene rubber, readily release hydrogen chloride and chlorinated organic compounds during heat treatment. This can not only corrode equipment but also affect the stability and safety of the resulting fuel. Therefore, in existing fuel preparation or waste plastic treatment technologies, chlorinated plastics and rubbers are often considered undesirable components, limiting their application in fuel production.

[0004] Furthermore, existing technologies typically treat different components as independent reaction objects when processing mixed waste plastics and rubber, failing to fully consider the potential mutual influences that may occur when multiple polymer materials are heated together. This can easily lead to uneven reaction processes, coking, and increased side reactions, thereby reducing overall conversion efficiency and fuel yield, and hindering the further promotion and application of related technologies.

[0005] Therefore, there is an urgent need for a fuel preparation method suitable for waste chlorinated mixed plastics and rubber. This method can achieve effective degradation and dechlorination of various polymer materials under relatively mild conditions, improve the yield and quality of liquid fuel products, and reduce energy consumption and equipment corrosion risks, thereby providing a new technical approach for the high-value utilization of waste chlorinated mixed plastics and rubber as fuel. Summary of the Invention

[0006] The purpose of this section is to outline some aspects of the embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0007] To address the aforementioned technical problems, according to one aspect of the present invention, the present invention provides the following technical solution: A method for preparing fuel oil using waste chlorine-containing polymer materials includes the following steps: S1: Pretreatment of waste chlorine-containing polymer materials and polystyrene; S2: Add the pretreated solid raw material obtained in S1 to the reactor, add the catalyst and mix evenly; S3: Under the action of a catalyst, the solid raw material undergoes a synergistic dechlorination and chain-breaking degradation reaction by one of the following methods: heating, ultrasonication, grinding, or mechanical ball milling; S4: After the reaction is complete, the reaction system is cooled and separated, and the liquid fuel oil product is collected.

[0008] As a preferred embodiment of the method for preparing fuel oil from waste chlorine-containing polymer materials according to the present invention, the pretreatment in S1 includes washing, drying, and cutting or crushing to form solid raw materials with uniform particle size or dimensions.

[0009] As a preferred embodiment of the method for preparing fuel oil using waste chlorine-containing polymer materials according to the present invention, the waste chlorine-containing polymer materials are post-consumer waste products, including one or more of powder, film, pipe, foam products, disposable lunch boxes, garbage bags, plastic bottles, and rubber rings.

[0010] As a preferred embodiment of the method for preparing fuel oil using waste chlorine-containing polymer materials according to the present invention, the waste chlorine-containing polymer materials are one or more of polyvinyl chloride, polyvinylidene chloride, and chloroprene rubber in any combination.

[0011] In a preferred embodiment of the method for preparing fuel oil using waste chlorine-containing polymer materials as described in this invention, the ratio of the mass of polystyrene to the total mass of the waste chlorine-containing polymer materials in step S1 is not less than 1 / 100.

[0012] As a preferred embodiment of the method for preparing fuel oil using waste chlorine-containing polymer materials according to the present invention, the catalyst in S2 is selected from one or more combinations of AlCl3, FeCl3, ZnCl2, TiCl4, BF3, Al2O3, and ZnO.

[0013] In a preferred embodiment of the method for preparing fuel oil using waste chlorine-containing polymer materials according to the present invention, the mass ratio of the catalyst to the waste chlorine-containing polymer materials is 0.01-10:1.

[0014] As a preferred embodiment of the method for preparing fuel oil from waste chlorine-containing polymer materials according to the present invention, in step S3, when heating is used, the reaction temperature is 30-260 ℃ and the reaction time is 0.25-10 h; when ultrasonication is used, the ultrasonication time is 0.25-10 h; when grinding or mechanical ball milling is used, the grinding or ball milling time is 0.25-10 h.

[0015] As a preferred embodiment of the method for preparing fuel oil using waste chlorine-containing polymer materials according to the present invention, the separation in step S4 includes one or more of the following: condensation collection, static layering, decantation, filtration, centrifugation, or solvent extraction, to obtain liquid fuel oil product.

[0016] Compared with the prior art, the beneficial effects of the present invention are: (1) Strong applicability: It can handle waste chlorine-containing mixed plastics and rubber systems with complex composition and difficult to sort, and achieve synergistic dechlorination and degradation transformation.

[0017] (2) The conditions are relatively mild: Compared with the traditional high-temperature pyrolysis route, the present invention can achieve the conversion at a lower temperature or by means of ultrasound / mechanical chemical method, which helps to reduce energy consumption and side reactions.

[0018] (3) High resource value: Liquid fuel oil products with hydrocarbons in a certain carbon number range can be obtained and can be used for fuel oil or fuel blending components.

[0019] (4) Safety and environmental friendliness: Dechlorination and conversion can reduce the adverse effects of chlorine-containing components on equipment corrosion and product quality, and have good engineering application potential. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and detailed embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein: Figure 1 This is a flowchart of a method for preparing fuel oil using waste chlorine-containing polymer materials according to the present invention; Figure 2 This is a photograph of the liquid fuel oil obtained in Example 1 of the method for preparing fuel oil using waste chlorine-containing polymer materials according to the present invention. Figure 3 This is a gel permeation chromatogram of liquid fuel oil prepared in Example 1 of the present invention, which describes a method for preparing fuel oil using waste chlorine-containing polymer materials. Detailed Implementation

[0021] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0022] Secondly, the present invention is described in detail with reference to the schematic diagrams. When detailing the embodiments of the present invention, for ease of explanation, the cross-sectional views illustrating the device structure may be partially enlarged, not according to the usual scale. Furthermore, the schematic diagrams are merely examples and should not limit the scope of protection of the present invention. In addition, actual fabrication should include three-dimensional spatial dimensions of length, width, and depth.

[0023] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0024] Please see Figure 1 This invention provides a method for preparing fuel oil using waste chlorine-containing polymer materials, comprising the following steps: S1: Pre-treat waste chlorine-containing polymer materials and polystyrene. The mass ratio of polystyrene to the total mass of waste chlorine-containing polymer materials is not less than 1 / 100. The pre-treatment includes washing, drying, and cutting or crushing to form solid raw materials with uniform particle size or dimensions. The waste chlorine-containing polymer materials are post-consumer waste products, including one or more of powder, film, pipe, foam products, disposable lunch boxes, garbage bags, plastic bottles, and rubber rings. The waste chlorine-containing polymer materials are any combination of one or more of polyvinyl chloride, polyvinylidene chloride, and chloroprene rubber. S2: Add the pretreated solid raw material obtained in S1 into the reactor, add the catalyst and mix evenly. The catalyst is selected from AlCl3, FeCl3, ZnCl2, TiCl4, BF3 and one or more combinations of Al2O3 and ZnO. The mass ratio of the catalyst to the waste chlorine-containing polymer material is 0.01-10:1. S3: Under the action of a catalyst, the solid raw material undergoes a synergistic dechlorination and chain-breaking degradation reaction by one of the following methods: heating, ultrasound, grinding, or mechanical ball milling. When heating is used, the reaction temperature is 30-260 ℃ and the reaction time is 0.25-10 h; when ultrasound is used, the ultrasound time is 0.25-10 h; when grinding or mechanical ball milling is used, the grinding or ball milling time is 0.25-10 h. S4: After the reaction is completed, the reaction system is cooled and separated to collect the liquid fuel oil product. The separation process includes one or more of the following: condensation collection, static layering, decantation, filtration, centrifugation, or solvent extraction, to obtain the liquid fuel oil product.

[0025] Example 1 The catalysts used in this example are AlCl3 and FeCl3.

[0026] The method is as follows: Step 1: Weigh 5 g of PVC powder and 0.0864 g of PS powder into a round-bottom flask and mix them thoroughly. Step 2: Add 0.1068 g of AlCl3 powder and 0.648 g of FeCl3 powder to a round-bottom flask and mix thoroughly again. Place the round-bottom flask containing the powder in an oil bath and reflux at 260°C. o Heat at C for 15 minutes; Step 3: After the reaction is complete, cool to room temperature, allow to stand, extract with solvent, and centrifuge the liquid oil product (see [link to product description]). Figure 2 ).

[0027] Compositional analysis of the above degradation products (see [link]). Figure 3 ): In this embodiment, the molecular weight distribution width of the liquid oil obtained in step 3 is Ð=3.973, and the main carbon number is concentrated in C7-C6. 21 .

[0028] Example 2 The catalyst used in this example is FeCl3.

[0029] The method is as follows: Step 1: Weigh 1 g of PVC powder, 0.708 g of CR rubber block and 0.864 g of PS foam block into a round-bottom flask and mix them evenly. Step 2: Add 0.648 g of FeCl3 powder to the round-bottom flask and mix thoroughly again; place the round-bottom flask containing the powder in an oil bath and reflux for 30 minutes. o Heat at C for 10 hours; Step 3: After the reaction is complete, cool to room temperature, let stand, extract with solvent, and centrifuge the liquid oil product.

[0030] Compositional analysis of the above degradation products: In this embodiment, the molecular weight distribution width of the liquid oil obtained in step 3 is 1.844, with the main carbon number concentrated in C. 15 -C 42 .

[0031] Example 3 The catalyst used in this example is ZnO.

[0032] The method is as follows: Step 1: Weigh 5 g of PVC pipe block and 0.864 g of PS foam block into a round-bottom flask and mix them thoroughly. Step 2: Add 2.61 g of ZnO powder to the round-bottom flask and mix thoroughly again; place the round-bottom flask containing the powder in an ultrasonic cleaner and reflux for 10 h. Step 3: After the reaction is complete, cool to room temperature, let stand, extract with solvent, and centrifuge the liquid oil product.

[0033] Compositional analysis of the above degradation products: In this embodiment, the molecular weight distribution width of the liquid oil obtained in step 3 is Ð=3.13, and the main carbon number is concentrated in C. 14 -C 38 .

[0034] Example 4 The catalysts used in this example are ZnCl2 and Al2O3.

[0035] Step 1: Weigh 0.5 g of PVC film and 0.864 g of PS foam block into an agate ball mill jar and mix them evenly. Step 2: Add 1.088 g of ZnCl2 powder and 2.45 g of Al2O3 powder to the ball mill jar and mix them thoroughly again; place the ball mill jar containing the above powder in a planetary ball mill and ball mill for 10 h. Step 3: After the reaction is complete, cool to room temperature, let stand, extract with solvent, and centrifuge the liquid oil product.

[0036] Compositional analysis of the above degradation products: In this embodiment, the molecular weight distribution width of the liquid oil obtained in step 3 is Ð=3.26, and the main carbon number is concentrated in C. 14 -C 39 .

[0037] Example 5 The catalyst used in this example is Al2O3.

[0038] Step 1: Weigh 0.5 g of PVC film sheet, 0.775 g of PVDC plastic block and 0.0432 g of PS plastic bottle into an agate ball mill jar and mix them evenly; Step 2: Add 2.45 g of Al2O3 powder to the ball mill jar and mix thoroughly again; place the ball mill jar containing the powder in a planetary ball mill and mill for 15 min. Step 3: After the reaction is complete, cool to room temperature, let stand, extract with solvent, and centrifuge the liquid oil product.

[0039] Compositional analysis of the above degradation products: In this embodiment, the molecular weight distribution width of the liquid oil obtained in step 3 is Ð=3.483, with the main carbon number concentrated in C. 15 -C 48 .

[0040] Example 6 The catalyst used in this example is TiCl4.

[0041] Step 1: Weigh 0.05 g of PVC pipe block, 0.775 g of PVDC plastic block, 0.708 g of CR rubber block and 0.864 g of PS plastic bottle into a round bottom flask and mix them evenly. Step 2: Place 15.17 g of TiCl4 powder into a round-bottom flask containing the above powder and sonicate it in an ultrasonic cleaner for 15 min. Step 3: After the reaction is complete, cool to room temperature, let stand, extract with solvent, and centrifuge the liquid oil product.

[0042] Compositional analysis of the above degradation products: In this embodiment, the molecular weight distribution width of the liquid oil obtained in step 3 is Ð=4.275, and the main carbon number is concentrated in C. 11 -C 43 .

[0043] Example 7 The catalyst used in this example is BF3.

[0044] Step 1: Weigh 25 g of PVC garbage bag and 0.864 g of PS plastic bottle into a round-bottom flask and mix them thoroughly. Step 2: Add 1.085 g of BF3 powder to the round-bottom flask and mix thoroughly again; place the round-bottom flask containing the powder in an oil bath and reflux at 60°C. o Heat at C for 8 hours; Step 3: After the reaction is complete, cool to room temperature, let stand, extract with solvent, and centrifuge the liquid oil product.

[0045] Compositional analysis of the above degradation products: In this embodiment, the molecular weight distribution width of the liquid oil obtained in step 3 is Ð=4.103, and the main carbon number is concentrated in C. 12 -C 47 .

[0046] In summary, the synergistic dechlorination degradation method provided by this invention can effectively convert waste chlorine-containing mixed plastics and rubber systems that are difficult to sort through thermal, ultrasonic, or mechanochemical means under the action of a catalyst, and obtain liquid fuel oil products, which has good prospects for industrial application.

[0047] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way.

[0048] Although the present invention has been described above with reference to embodiments, various modifications can be made and components can be replaced with equivalents without departing from the scope of the invention. In particular, as long as there is no structural conflict, the features in the disclosed embodiments can be combined with each other in any manner. The lack of an exhaustive description of these combinations in this specification is merely for the sake of brevity and resource conservation. Therefore, the present invention is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A method for preparing fuel oil using waste chlorine-containing polymer materials, characterized in that, Includes the following steps: S1: Pretreatment of waste chlorine-containing polymer materials and polystyrene; S2: Add the pretreated solid raw material obtained in S1 to the reactor, add the catalyst and mix evenly; S3: Under the action of a catalyst, the solid raw material undergoes a synergistic dechlorination and chain-breaking degradation reaction by one of the following methods: heating, ultrasonication, grinding, or mechanical ball milling; S4: After the reaction is complete, the reaction system is cooled and separated, and the liquid fuel oil product is collected.

2. The method for preparing fuel oil using waste chlorine-containing polymer materials according to claim 1, characterized in that, The pretreatment in S1 includes washing, drying, and cutting or crushing to form solid raw materials with uniform particle size or dimensions.

3. The method for preparing fuel oil using waste chlorine-containing polymer materials according to claim 1, characterized in that, The waste chlorine-containing polymer material is a post-consumer waste product, which includes one or more of the following: powder, film, pipe, foam product, disposable lunch box, garbage bag, plastic bottle, and rubber ring.

4. The method for preparing fuel oil using waste chlorine-containing polymer materials according to claim 2, characterized in that, The waste chlorine-containing polymer material is one or more of polyvinyl chloride, polyvinylidene chloride, and chloroprene rubber, or any combination thereof.

5. The method for preparing fuel oil using waste chlorine-containing polymer materials according to claim 1, characterized in that, The ratio of the mass of polystyrene in S1 to the total mass of waste chlorine-containing polymer materials shall not be less than 1 / 100.

6. The method for preparing fuel oil using waste chlorine-containing polymer materials according to claim 1, characterized in that, The catalyst in S2 is selected from one or more combinations of AlCl3, FeCl3, ZnCl2, TiCl4, BF3, Al2O3, and ZnO.

7. A method for preparing fuel oil using waste chlorine-containing polymer materials according to claim 6, characterized in that, The mass ratio of the catalyst to the waste chlorine-containing polymer material is 0.01-10:

1.

8. The method for preparing fuel oil using waste chlorine-containing polymer materials according to claim 1, characterized in that, In step S3, when heating is used, the reaction temperature is 30-260 ℃ and the reaction time is 0.25-10 h; when ultrasonication is used, the ultrasonication time is 0.25-10 h; when grinding or mechanical ball milling is used, the grinding or ball milling time is 0.25-10 h.

9. A method for preparing fuel oil using waste chlorine-containing polymer materials according to claim 1, characterized in that, The separation process in S4 includes one or more of the following: condensation and collection, settling and layering, decantation, filtration, centrifugation, or solvent extraction, to obtain liquid fuel oil products.

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