Method for preparing gaseous fuel by FCC waste rubber residue catalytic waste polyolefin plastic hydrothermal cracking
By ion exchange and calcination of FCC waste plastic residue, and utilizing the rare earth elements and iron within it as hydrogenation active sites, the problems of pollution from FCC waste plastic residue treatment and high cost of precious metal catalysts have been solved, and the efficient hydrogenation pyrolysis of waste polyolefin plastics to produce high-value gaseous fuels has been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHANGZHOU UNIV
- Filing Date
- 2024-07-12
- Publication Date
- 2026-08-04
AI Technical Summary
In existing technologies, the treatment of FCC waste plastic residue leads to environmental pollution and resource waste. At the same time, precious metal catalysts are expensive and difficult to efficiently produce high-value gaseous fuels in the hydrogenation pyrolysis of waste polyolefin plastics.
Using inexpensive and readily available FCC waste plastic residue containing rare earth elements as a catalyst, and through ion exchange and roasting treatment, the rare earth elements and iron in the residue are used as hydrogenation active sites to perform hydrogenation pyrolysis of waste polyolefin plastics to produce gaseous fuel.
The efficient catalytic production of gaseous fuels under lower temperature and pressure conditions reduces catalyst costs and improves the selectivity and yield of gaseous fuels, thus realizing the resource utilization of FCC waste rubber residue.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of waste plastic upgrading and recycling, and in particular to a method for preparing gaseous fuel by catalytic hydrogenation and pyrolysis of waste polyolefin plastics from FCC waste plastic residue. Background Technology
[0002] To upgrade and recycle waste polyolefin plastics, early methods primarily employed direct pyrolysis and catalytic pyrolysis. Direct pyrolysis utilizes intense heat to break the C-C bonds in polyolefin plastics under catalyst-free and oxygen-free conditions. However, direct pyrolysis involves high reaction temperatures (500–900℃), high energy consumption, and the products are thermodynamically controlled, exhibiting low selectivity and a wide carbon number distribution (C1–C2). 60 The process of converting PE into high-value-added products is difficult. Catalytic pyrolysis, which involves adding catalysts such as zeolite molecular sieves during pyrolysis, reduces the reaction temperature to some extent compared to direct pyrolysis, but still suffers from problems such as easy catalyst carbonization and a wide carbon number distribution in the products. In recent years, hydropyrolysis has attracted widespread attention from scholars because it can significantly reduce the reaction temperature, effectively solve the problem of catalyst carbonization, and reduce the carbon number distribution in the products. However, most of the existing reported hydrolysis catalysts use precious metals such as Pt and Ru as catalytic sites, which are expensive and have significant limitations. Guido Zichittella et al. (JACSAu, 2022, 2, 2259-2268) used Co / ZSM-5 as a catalyst to convert PE into propane-based gaseous products under relatively mild conditions, with a gas yield as high as 95%. However, their reaction required a large amount of ZSM-5, with a ZSM-5 mass ratio of 0.7 to 1.4 to PE. However, the high cost of commercially available ZSM-5 limits the large-scale application of this method. Wei-Tse Lee et al. (Cell Reports Physical Science 2, 100332) prepared a Ru-modified zeolite that can catalyze the conversion of polyethylene, polypropylene, and polystyrene to methane (purity >97%) at 300–350 °C and 5 MPa H₂ pressure. However, the catalyst they used still suffers from excessive cost, with the loading of the precious metal Ru reaching 2.5%. Therefore, developing a low-cost and efficient catalyst is of significant application value for realizing the conversion of polyolefin plastics into high-value products.
[0003] Fully catalyzed cracking catalysts (FCC catalysts) are widely used in secondary petroleum processing. The production of FCC catalysts generates large amounts of wastewater containing significant amounts of suspended solids, which cannot be directly discharged. To ensure compliance with wastewater discharge standards, the suspended solids in the wastewater must undergo sedimentation, filtration, and slag removal processes, resulting in a large quantity of FCC catalyst waste residue (FCC waste residue), primarily composed of Al2O3 and SiO2. my country produces approximately 230,000 tons of FCC catalysts annually, and along with this production, approximately 80,000 tons of FCC waste residue are discharged annually. Currently, FCC waste residue is mainly treated through landfill, a method that leads to severe environmental pollution, economic burden, and resource waste. Using FCC waste residue as a catalyst for the hydrogenation pyrolysis of waste polyolefin plastics can both upgrade and recycle waste polyolefin plastics and promote the resource reuse of FCC waste residue.
[0004] Patent CN202211607465.4 discloses a catalyst for the catalytic cracking of waste plastics and its preparation method. This method involves acid leaching, pore-expansion modification, and loading with metal oxides onto an FCC waste catalyst, which is then used to pyrolyze mixed waste plastics at 500°C to produce liquid fuel. Patent CN202211391419.5 discloses a method for catalytic cracking of polymers using an FCC discharge agent. This method involves alkali treatment and ammonium salt modification of an FCC waste catalyst, followed by pyrolysis of chlorine-containing waste plastics to produce cracked oil. Patent CN201810312024.9 discloses a method for catalytic cracking of polymers using an FCC discharge agent. This method involves grinding, acid washing, high-temperature steam cleaning, or high-temperature calcination of the FCC discharge agent, followed by pyrolysis of waste plastics to obtain cracked oil. The methods described above all use FCC waste catalysts or FCC discharge agents, which are partially deactivated FCC catalysts. They employ catalytic pyrolysis, which requires high temperatures (400-500℃) to achieve a high pyrolysis oil yield (71-86%). Furthermore, the obtained pyrolysis oil is of poor quality and has a complex composition, with the main component being low-value-added heavy oil.
[0005] How to use FCC waste residue, i.e. the waste residue generated during the FCC preparation process, as a raw material to prepare a catalyst? Using the hydropyrolysis method, the gas yield is high at a relatively low reaction temperature, and the main components are high-value propane and butane. This has not been reported in the existing technology. Summary of the Invention
[0006] To address the shortcomings of existing technologies, this invention aims to provide a method for the catalytic hydrogenation and pyrolysis of waste polyolefin plastics from FCC waste rubber residue to produce gaseous fuels. This invention uses inexpensive and readily available FCC waste rubber residue containing rare earth elements as a catalyst, utilizing rare earth elements (lanthanum, cerium) and iron in the FCC waste rubber as active hydrogenation sites. It achieves efficient catalytic hydrogenation and pyrolysis of waste polyolefin plastics to produce gaseous fuels under relatively low temperature and pressure conditions without the need for loading other metals. This invention is simple to operate and operates under mild reaction conditions, providing a solution for the upgrading and recycling of waste polyolefin plastics.
[0007] The technical solution adopted by this invention to solve its technical problem is:
[0008] FCC waste resin containing rare earth elements was dried to constant weight and then calcined in a muffle furnace at 500–600℃ for 4–6 hours. It was then placed in a 1 mol / L ammonium chloride solution and impregnated with stirring at a specific temperature for ion exchange. The impregnated FCC waste resin was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste resin was then calcined in a muffle furnace at 500–600℃ for 2–4 hours. This process of ammonium chloride impregnation, washing, drying, and calcination was repeated 3–5 times to achieve a high degree of ion exchange, yielding the FCC waste resin catalyst.
[0009] The concentration of the ammonium chloride solution is 0.5–2 mol / L; the ratio of FCC waste glue residue to ammonium chloride solution is 1 g / (5–20) mL; the impregnation temperature is 70–90℃, and the time is 1–2 h.
[0010] The dry-based FCC waste adhesive residue, based on a total mass of 100%, contains 5%–25% Al (calculated as Al2O3), 40%–70% Si (calculated as SiO2), 2%–12% La (calculated as La2O3), 5%–15% Ce (calculated as CeO2), and 0.1%–2% Fe (calculated as Fe2O3). Other impurities are present in small quantities and can be ignored.
[0011] The FCC waste rubber residue catalyst and waste polyolefin plastic were mixed evenly and loaded into a stainless steel high-pressure reactor. A magnetic stirrer was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas at 1–5 MPa was introduced, and the reaction was carried out at 250–350 °C for 8–36 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag, and the mixture of pyrolysis oil and catalyst in the reactor was collected using a sample bottle. The liquid product was extracted with cyclohexane or toluene. The gaseous and liquid products were further analyzed by gas chromatography.
[0012] Furthermore, the mass ratio of FCC waste rubber residue catalyst to waste polyolefin plastic is 0.2 to 1.4.
[0013] Preferably, the mass ratio of the FCC waste rubber residue catalyst to waste polyolefin plastic is 0.6 to 1.2.
[0014] Preferably, the reaction temperature is 300–330°C.
[0015] Preferably, the initial hydrogen pressure is 2 to 3 MPa.
[0016] Preferably, the reaction time is 20 to 36 hours.
[0017] The main product is gaseous fuel, specifically C1-C5 alkane gaseous fuel. A small amount of liquid fuel is also produced, specifically C4-C5 alkane gaseous fuel. 12 Alkanes.
[0018] Beneficial effects of the present invention
[0019] (1) The present invention uses FCC waste gum residue after ion exchange as a catalyst, and utilizes rare earth elements (lanthanum, cerium) and iron in FCC waste gum residue as hydrogenation active sites, without the need to load other metals. Compared with the prior art, the present invention greatly reduces the manufacturing cost of the catalyst.
[0020] (2) Hydrogenation pyrolysis is an acidic catalytic reaction. After ion exchange, the FCC waste rubber residue improves the selectivity and yield of gaseous fuels.
[0021] (3) Using FCC waste rubber residue as a catalyst for the hydrogenation and pyrolysis of waste polyolefin plastics to prepare gaseous fuel provides an effective way for the efficient utilization of FCC waste rubber residue solid waste. Attached Figure Description
[0022] Figure 1 This is the XRD pattern of FCC waste adhesive residue.
[0023] Figure 2 This is a gas chromatogram of the gaseous product of Example 3. Detailed Implementation
[0024] The present invention will be further described with reference to the following embodiments, but it should be understood that these embodiments are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.
[0025] The FCC waste adhesive residue used in the specific embodiments of this invention is sourced from China Petroleum & Chemical Corporation Qilu Branch. The compositional analysis of the FCC waste adhesive residue is as follows:
[0026] FCC waste glue residue was placed in an oven and dried at 120℃ for 48 hours to remove excess moisture. The main components of the FCC waste glue residue were analyzed by X-ray fluorescence spectroscopy. The mass fraction of oxides in the FCC waste glue residue was 51.1% SiO2, 18.9% Al2O3, 9.6% CeO2, 6.5% La2O3, 5.8% Na2O, 2.6% GaO, 0.8% MgO, and 0.4% Fe2O3. Other impurities accounted for a small proportion and could be ignored.
[0027] Example 1
[0028] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0029] 1.5g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 330℃ for 8 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0030] Example 2
[0031] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0032] 1.5g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 330℃ for 20 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0033] Example 3
[0034] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0035] 1.5g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 330℃ for 36 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0036] Example 4
[0037] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0038] 1.5g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 250℃ for 24 hours. After the reaction was completed, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0039] Example 5
[0040] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0041] 1.5g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. The air inside the reactor was then replaced with hydrogen five times. Afterward, hydrogen was introduced at 3MPa, and the reaction was carried out at 330℃ for 24 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0042] Example 6
[0043] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0044] 1.5g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 350℃ for 24 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0045] Example 7
[0046] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0047] 0.3g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 330℃ for 24 hours. After the reaction was completed, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0048] Example 8
[0049] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0050] 1.8g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 330℃ for 24 hours. After the reaction was completed, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0051] Example 9
[0052] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0053] 2.1g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 330℃ for 24 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0054] Example 10
[0055] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0056] 1.5g of FCC waste gum residue catalyst and 1.5g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. The air inside the reactor was then replaced with hydrogen five times. Afterward, 1MPa of hydrogen was introduced, and the reaction was carried out at 330℃ for 24 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0057] Example 11
[0058] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0059] 3g of FCC waste gum residue catalyst and 3g of LDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas at 5 MPa was introduced, and the reaction was carried out at 330℃ for 12 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0060] Example 12
[0061] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0062] 1.5g of FCC waste rubber residue catalyst and 1.5g of PP were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas at 3MPa was introduced, and the reaction was carried out at 330℃ for 12 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0063] Example 13
[0064] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0065] 1.5g of FCC waste rubber residue catalyst and 1.5g of PP were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas at 3MPa was introduced, and the reaction was carried out at 330℃ for 24 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0066] Example 14
[0067] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0068] 1.5g of FCC waste adhesive residue catalyst and 1.5g of HDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen was introduced at 3MPa, and the reaction was carried out at 330℃ for 24 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0069] Example 15
[0070] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0071] 1.5g of FCC waste adhesive residue catalyst and 1.5g of HDPE were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 330℃ for 32 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0072] Example 16
[0073] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0074] 1.5g of FCC waste gum residue catalyst and 1.5g of PS were mixed thoroughly and loaded into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 330℃ for 24 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0075] Example 17
[0076] FCC waste rubber residue was dried to constant weight and then calcined in a muffle furnace at 550℃ for 5 hours. 30g of the calcined FCC waste rubber residue was then placed in 300ml of a 1mol / L ammonium chloride solution and impregnated at 90℃ for 1.5 hours with stirring. The impregnated FCC waste rubber residue was repeatedly washed and filtered with hot deionized water, then dried in a forced-air oven. The dried FCC waste rubber residue was then calcined in a muffle furnace at 550℃ for 3 hours. This impregnation, washing, drying, and calcination process was repeated five times to obtain the FCC waste rubber residue catalyst.
[0077] 1.5g of FCC waste rubber residue catalyst, 0.75g of LDPE, and 0.75g of PP were mixed thoroughly and placed into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3MPa, and the reaction was carried out at 330℃ for 24 hours. After the reaction was completed, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle, and the liquid product was extracted with cyclohexane or toluene. The gaseous and liquid products were further analyzed by gas chromatography.
[0078] Compare with Example 1
[0079] 1.5 g of commercial HY catalyst (purchased from Nankai University Catalyst Factory) and 1.5 g of LDPE were mixed thoroughly and placed into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3 MPa, and the reaction was carried out at 330 °C for 24 h. After the reaction was completed, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample vial, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0080] Compare with Example 2
[0081] 1.5 g of commercial Hβ catalyst (purchased from Nankai University Catalyst Factory) and 1.5 g of LDPE were mixed thoroughly and placed into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air inside the reactor was replaced with hydrogen five times. Afterward, hydrogen gas was introduced at 3 MPa, and the reaction was carried out at 330 °C for 24 h. After the reaction was completed, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag. The pyrolysis oil and catalyst mixture in the reactor was collected using a sample vial, and the liquid product was extracted with cyclohexane or toluene. The gas and liquid products were further analyzed by gas chromatography.
[0082] Compare with Example 3
[0083] Unexchanged FCC waste rubber residue (referring to FCC waste rubber residue that has not been impregnated in ammonium chloride, dried to constant weight, and then calcined in a muffle furnace at 550℃ for 5 hours to serve as an FCC waste rubber residue catalyst) was mixed thoroughly with 1.5g of LDPE and placed into a stainless steel high-pressure reactor. A magnetic stir bar was added, and the reactor was sealed. Subsequently, the air in the reactor was replaced with hydrogen five times. Then, 3MPa of hydrogen was introduced, and the reaction was carried out at 330℃ for 24 hours. After the reaction, the reactor was placed in a water bath. Once the reactor temperature cooled to room temperature, the pyrolysis gas was collected using a gas collection bag, and the pyrolysis oil and catalyst mixture in the reactor was collected using a sample bottle. The liquid product was extracted with cyclohexane or toluene. The gas and liquid phase products were further analyzed by gas chromatography.
[0084] Table 1. Conversion rates and product yields of the reactions in Examples 1-17 and the control examples.
[0085]
[0086]
[0087] Table 2. Composition of gaseous fuels in Examples 1-17 and Comparative Examples.
[0088]
[0089]
[0090] The feed conversion rates and product yields obtained from the above examples and comparative examples are shown in Table 1; the gas phase composition is shown in Table 2. The results show that the FCC waste rubber residue exhibits superior catalytic activity, with the conversion rates of each feedstock essentially reaching 100%, and the composition mainly consisting of propane and butane, which have higher added value. Under the conditions of a catalyst-to-feedstock mass ratio of 1, a temperature of 330℃, a time of 24h, and an initial hydrogen pressure of 3MPa, the feedstock conversion rate reaches 100%. The highest gaseous fuel yield reaches 95.3%. As can be seen from Example 5 and Comparative Examples 1 and 2, under the conditions of a catalyst-to-feedstock mass ratio of 1, a reaction temperature of 330℃, a time of 24h, and an initial hydrogen pressure of 3MPa, the feedstock conversion rates of Example 5, Comparative Examples 1 and 2 are 100%, 97.6%, and 99.0%, respectively, and the gaseous fuel yields are 91.8%, 81.3%, and 83.0%, respectively. The catalytic activity of the FCC waste rubber residue is superior to that of commercial HY and Hβ catalysts. As can be seen from Example 5 and Comparative Example 3, the catalytic performance of FCC waste rubber residue was greatly improved after ion exchange, and the gas yield increased from 18.8% to 91.8%.
[0091] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.
Claims
1. A method for preparing gaseous fuel from FCC spent rubber residue catalytic waste old polyolefin plastic by hydro-thermal pyrolysis, characterized in that, The method steps are as follows: After being roasted and ion-exchanged, FCC waste rubber residue is used as a catalyst and mixed with waste polyolefin plastics in a certain proportion. The mixture is then loaded into a reactor and subjected to hydrogenation pyrolysis under a hydrogen atmosphere. After the reaction is completed, the gaseous fuel and liquid fuel are collected separately. The preparation method of FCC waste rubber residue as a catalyst after calcination and ion exchange is as follows: the FCC waste rubber residue is dried to constant weight and then placed in a muffle furnace and calcined at 500~600℃ for 4~6h. Then it is placed in ammonium chloride solution and stirred and impregnated at a certain temperature to carry out ion exchange. The impregnated FCC waste rubber residue is washed and dried, and then calcined in a muffle furnace at 500~600℃ for 2~4 hours. The impregnation, washing, drying and calcination process is repeated 3~5 times to obtain the ion-exchanged FCC waste rubber residue catalyst. The dry-based FCC waste rubber residue, based on a total mass of 100%, contains 5%–25% Al (calculated as Al2O3), 40%–70% Si (calculated as SiO2), 2%–12% La (calculated as La2O3), 5%–15% Ce (calculated as CeO2), and 0.1%–2% Fe (calculated as Fe2O3).
2. The process for preparing gaseous fuel from FCC spent rubber residue catalytic waste and old polyolefin plastic by hydro-thermal pyrolysis according to claim 1, characterized by: The ammonium chloride solution concentration was 1 mol / L; the immersion conditions were immersion at 70–90℃ for 1–2 hours.
3. The process for preparing gaseous fuel from FCC spent rubber residue catalytic waste and old polyolefin plastic by hydro-thermal pyrolysis according to claim 1, characterized in that, The waste polyolefin plastic is one or a mixture of two or more of low-density polyethylene, high-density polyethylene, polypropylene, and polystyrene.
4. The process for preparing gaseous fuel from FCC spent rubber residue catalytic waste and old polyolefin plastic by hydro-thermal pyrolysis according to claim 1, characterized in that, The mass ratio of the FCC waste plastic residue to waste polyolefin plastic is 0.2 to 1.
4.
5. The process for preparing gaseous fuel from FCC spent rubber residue catalytic waste and old polyolefin plastic by hydro-thermal pyrolysis according to claim 1, characterized in that, The reaction temperature of the hydrogenation pyrolysis is 250–350°C, the initial hydrogen pressure is 1–5 MPa, and the reaction time is 8–36 h.
6. The process for preparing gaseous fuel from FCC spent rubber residue catalytic waste and old polyolefin plastic by hydro-thermal pyrolysis according to claim 1, characterized in that, The reaction temperature for the hydrogenation pyrolysis is 300–330°C, the initial hydrogen pressure is 2–3 MPa, and the reaction time is 20–36 h.
7. The process for preparing gaseous fuel from FCC spent rubber residue catalytic waste and old polyolefin plastic by hydro-thermal pyrolysis according to claim 1, characterized in that, The ratio of the FCC waste glue residue to the ammonium chloride solution is 1 g / (5-20) mL.
8. The process for preparing gaseous fuel from FCC spent rubber residue catalytic waste and old polyolefin plastic by hydro- pyrolysis as claimed in claim 1, wherein, The gaseous fuel is a C1-C5 alkane gaseous fuel.