Method for producing hydrogen by taking polycarbonate plastic as raw material
By using Rainey catalysts and polycarbonate plastics under mild conditions, the hydrogen production challenges of catalyst deactivation and high-temperature conditions are solved, and efficient and environmentally friendly hydrogen production is achieved, reducing process costs and providing Environmentally friendly hydrogen production path.
Patent Information
- Application Number
- CN202310848685.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-07-10
- Publication Date
- 2025-01-10
AI Technical Summary
The prior art has the problem of catalyst deactivation in the process of catalyzing plastic hydrogen production under high temperature conditions, and efficient catalyzing of plastic hydrogen production under mild conditions faces huge challenges.
The Rainy-type catalyst is used to react with polycarbonate plastic and water in a closed pressure vessel, and hydrogen is prepared catalyzed under mild conditions of 250-350°C using an inactive atmosphere. The catalyst can be centrifuged and recycled.
It has achieved efficient catalytic conversion of polycarbonate plastics under mild conditions to prepare hydrogen, reducing process costs, providing an environmentally friendly hydrogen production path, solving the problem of plastic waste accumulation, and providing guarantees for the sustainable development of the economy and the environment.
Smart Images
Figure CN119284835A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to a method for producing hydrogen using polycarbonate plastic as raw material, belonging to the field of hydrogen production. Background Art
[0002] Since Baekelan successfully synthesized the first synthetic polymer through the condensation reaction of formaldehyde and phenol in 1907, plastic polymers have penetrated into every aspect of our lives. With the continuous advancement of science and technology in modern society, plastics play an increasingly important role in packaging, construction, medical care, electronics, transportation and other fields. As one of the top ten plastics in the world, polycarbonate is an important polymer synthetic material with an annual global output of about 6 million tons. Polycarbonate is a plastic with excellent physical and mechanical properties, which makes it widely used in fields with high light transmittance requirements. However, due to the chemical inertness of plastic products, a large amount of plastic waste has accumulated on land and in the ocean, causing serious damage to the ecological environment. In view of the current problem of poor mechanical recycling performance, chemical recycling is considered to be one of the most promising technologies.
[0003] At present, there are two main methods proposed for producing hydrogen using waste plastics as raw materials, namely gasification and pyrolysis. Gasification refers to the process of converting waste plastics into a gas mixture through a thermochemical reaction of incomplete combustion in the temperature range of 800-1300°C using water vapor, oxygen-rich, pure oxygen or air as the gasification medium. Pyrolysis refers to the process of converting waste plastics into a gas mixture in the temperature range of 400-800°C under oxygen-deficient or oxygen-free conditions. Gasification and pyrolysis usually include two steps: one is that the waste plastics are converted into raw gas through gasification / pyrolysis, and the other is that the raw gas is steam reformed on the catalyst to produce a gas mixture (H2, CO, CO2 and CH4, etc.). Both processes require high temperatures. In addition, the effects of different catalysts on the proportion of hydrogen in the gas mixture have also been studied. However, in the steam reforming stage of the raw gas, the catalyst is easily deactivated due to coke deposition. Therefore, high operating temperature and catalyst deactivation are the main limiting factors for hydrogen production from plastics, and efficient catalytic hydrogen production from plastics under mild conditions still faces great challenges. Summary of the invention
[0004] The present invention develops a method for producing hydrogen using polycarbonate plastic as raw material, realizing a revolutionary technology for preparing hydrogen from discarded polycarbonate plastic under mild conditions, providing important guarantees for the sustainable development of my country's environment and economy, and opening up a new path for hydrogen production.
[0005] According to one aspect of the present application, there is provided a method for producing hydrogen using polycarbonate plastic as raw material, comprising the following steps:
[0006] The raw materials containing polycarbonate plastic, Raney-type catalyst and water are reacted in a sealed pressure vessel under an inert gas atmosphere to obtain a product containing hydrogen.
[0007] The polycarbonate plastic is selected from at least one of polycarbonate powder, polycarbonate particles, optical disks, polycarbonate tubes, and polycarbonate sheets.
[0008] The Raney-type catalyst is selected from at least one of Raney Ni, Raney Ni-Al, Raney Ni-Mo, Raney Ni-Sn, Raney Ni-Fe, and Raney Ni-Cu.
[0009] The mass of the Raney-type catalyst is 20-70wt% of the mass of the polycarbonate plastic;
[0010] Optionally, the mass of the Raney-type catalyst is 50-70 wt % of the mass of the polycarbonate plastic.
[0011] Optionally, the mass of the Raney-type catalyst is any value of 50wt%, 60wt%, 70wt% of the mass of the polycarbonate plastic, or a range of values therebetween.
[0012] The inert gas atmosphere is selected from at least one of nitrogen, argon and helium.
[0013] The pressure of the inert gas atmosphere is 0.1-7 MPa;
[0014] Optionally, the pressure of the inert gas atmosphere is 0.1 to 4 MPa;
[0015] Optionally, the pressure of the inert gas atmosphere is 0.1-2 MPa.
[0016] Optionally, the pressure of the inert gas atmosphere is any value among 0.1 MPa, 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, or a range between any two values.
[0017] The reaction temperature is 250-350°C;
[0018] Optionally, the reaction temperature is 280-350°C;
[0019] Optionally, the reaction temperature is 300-350°C.
[0020] Optionally, the reaction temperature is any value of 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, or any range therebetween.
[0021] The reaction time is 0.05 to 24 hours;
[0022] Optionally, the reaction time is 0.05 to 10 h;
[0023] Optionally, the reaction time is 0.5 to 10 hours.
[0024] Optionally, the reaction time is any value among 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or a range between any two of them.
[0025] The Raney-type catalyst includes a Raney-type catalyst which is separated and reused after participating in the reaction.
[0026] The beneficial effects of this application include:
[0027] 1) The method described in the present application directly catalytically converts polycarbonate waste plastics under mild conditions to produce hydrogen, wherein the hydrogen production can be as high as This process not only solves the environmental problems caused by the massive accumulation of plastic waste, but also produces hydrogen, providing important guarantees for the sustainable development of my country's environment and economy and opening up a new path for hydrogen production.
[0028] 2) The catalyst used in the present invention can be centrifugally separated and further recycled, thereby reducing the cost of the preparation process.
[0029] 3) The present invention provides a method for producing hydrogen using polycarbonate plastics. The process is environmentally friendly, simple in process, easy to operate, and has high processing efficiency. The process is green and pollution-free, and is an environmentally friendly process. DETAILED DESCRIPTION
[0030] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.
[0031] The Raney-type catalysts in the embodiments of the present application: Raney Ni, Raney Ni-Mo, Raney Ni-Al, Raney Ni-Sn, Raney Ni-Fe and Raney Ni-Cu are obtained by activating their alloy powders. Take an appropriate amount of alloy powder and add 20wt% sodium hydroxide solution in an oil bath for 1 hour. After the reaction is completed, wash with water until neutral to obtain the corresponding Raney-type catalyst, which is used in the catalytic reaction.
[0032] The hydrogen production in the present embodiment is calculated as follows:
[0033]
[0034] Example 1
[0035] Weigh 0.22g of Raney Ni-Fe catalyst and add it to a 50mL reactor, and add 0.4g of raw polycarbonate powder and 10mL of water. Seal the reactor, fill it with N2 3-5 times, exhaust the air in the reactor, and finally fill it with nitrogen to atmospheric pressure. Heat to 300℃ by electric heating under 800rpm magnetic stirring and react for 5h. After the reaction is completed, stop stirring, cool the reactor to room temperature in an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, use an air bag to collect the reaction gas, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0036] The hydrogen production is
[0037] Example 2
[0038] Weigh 0.24g of Raney Ni-Fe catalyst and add it to a 50mL reactor, and add 0.4g of raw polycarbonate powder and 10mL of water. Seal the reactor, fill it with N2 3-5 times, exhaust the air in the reactor, and finally fill it with 1MPa of N2. Heat it to 330℃ with electric heating under 800rpm magnetic stirring and react for 4h. After the reaction is completed, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, use an air bag to collect the reaction gas, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0039] The hydrogen production is
[0040] Example 3
[0041] Weigh 0.26g of Raney Ni-Fe catalyst and add it to a 50mL reactor, and add 0.4g of raw polycarbonate powder and 10mL of water. Seal the reactor, fill it with N2 3-5 times, exhaust the air in the reactor, and finally fill it with 1MPa of N2. Heat it to 310℃ with electric heating under 800rpm magnetic stirring and react for 5h. After the reaction is completed, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, use an air bag to collect the reaction gas, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0042] The hydrogen production is
[0043] Example 4
[0044] Weigh 0.28g of Raney Ni-Fe catalyst and add it to a 50mL reactor. At the same time, add 0.4g of raw polycarbonate powder and 10mL of water to seal the reactor. Fill the reactor with N2 for 3-5 times, exhaust the air in the reactor, and finally fill it with nitrogen to atmospheric pressure. Heat to 300℃ with electric heating under 800rpm magnetic stirring and react for 5h. After the reaction, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, collect the reaction gas with an air bag, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0045] The hydrogen production is
[0046] Example 5
[0047] Weigh 0.28g of Raney Ni-Fe catalyst and add it to a 50mL reactor. At the same time, add 0.6g of raw polycarbonate powder and 10mL of water to seal the reactor. Fill the reactor with N2 for 3-5 times, exhaust the air in the reactor, and finally fill it with nitrogen to atmospheric pressure. Heat to 300℃ with electric heating under 800rpm magnetic stirring and react for 5h. After the reaction, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, collect the reaction gas with an air bag, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0048] The hydrogen production is
[0049] Example 6
[0050] Weigh 0.28g of Raney Ni-Fe catalyst and add it to a 50mL reactor. At the same time, add 1.0g of raw polycarbonate powder and 10mL of water to seal the reactor. Fill the reactor with N2 for 3-5 times, exhaust the air in the reactor, and finally fill it with nitrogen to atmospheric pressure. Heat to 300℃ with electric heating under 800rpm magnetic stirring and react for 5h. After the reaction, stop stirring, cool the reactor to room temperature with an ice-water bath, and record the reaction termination temperature and pressure. Open the gas outlet, collect the reaction gas with an air bag, and perform gas phase analysis. Add water to the reactor to remove the catalyst after the reaction, centrifuge it, and further recycle it.
[0051] The hydrogen production is
[0052] Example 7
[0053] The preparation process described in Example 1 was repeated, except that the polycarbonate powder was replaced with polycarbonate pellets, and the hydrogen production was obtained to be
[0054] Example 8
[0055] The preparation process described in Example 1 was repeated, except that the polycarbonate powder was replaced by optical disk, and the hydrogen production was obtained to be
[0056] Example 9
[0057] The preparation process described in Example 1 was repeated, except that the polycarbonate powder was replaced with a polycarbonate tube, and the hydrogen production was obtained.
[0058] Example 10
[0059] The preparation process described in Example 1 was repeated, except that the polycarbonate powder was replaced with polycarbonate sheets, and the hydrogen production was obtained to be
[0060] Embodiment 11
[0061] The preparation process described in Example 2 was repeated, except that the volume of the solvent water was changed to 8 mL, and the hydrogen yield was obtained as follows:
[0062] Example 12
[0063] The preparation process described in Example 2 was repeated, except that the volume of solvent water was changed to 6 mL, and the hydrogen yield was obtained as follows:
[0064] Embodiment 13
[0065] The preparation process described in Example 2 was repeated, except that the volume of the solvent water was changed to 4 mL, and the hydrogen yield was obtained as follows:
[0066] Embodiment 14
[0067] The preparation process described in Example 2 was repeated, except that the Raney Ni-Fe catalyst was replaced by a Raney Ni catalyst, and the hydrogen production was obtained to be
[0068] Embodiment 15
[0069] The preparation process described in Example 2 was repeated, except that the Raney Ni-Fe catalyst was replaced by the Raney Ni-Mo catalyst, and the hydrogen production was obtained.
[0070] Example 16
[0071] The preparation process described in Example 2 was repeated, except that the Raney Ni-Fe catalyst was replaced by a Raney Ni-Sn catalyst, and the hydrogen production was obtained.
[0072] Embodiment 17
[0073] The preparation process described in Example 2 was repeated, except that the Raney Ni-Fe catalyst was replaced by the Raney Ni-Al catalyst, and the hydrogen production was obtained.
[0074] Embodiment 18
[0075] The preparation process described in Example 2 was repeated, except that the Raney Ni-Fe catalyst was replaced by the Raney Ni-Cu catalyst, and the hydrogen production was obtained.
[0076] Embodiment 19
[0077] The preparation process described in Example 3 was repeated, except that the nitrogen pressure was changed to 0.1 MPa, and the hydrogen production was obtained.
[0078] Embodiment 20
[0079] The preparation process described in Example 3 was repeated, except that the nitrogen pressure was changed to 1.5 MPa, and the hydrogen production was obtained.
[0080] Embodiment 21
[0081] The preparation process described in Example 3 was repeated, except that the nitrogen pressure was changed to 2.0 MPa, and the hydrogen production was obtained.
[0082] Embodiment 22
[0083] The preparation process described in Example 3 was repeated, except that the nitrogen pressure was changed to 2.5 MPa, and the hydrogen production was obtained.
[0084] Embodiment 23
[0085] The preparation process described in Example 4 was repeated, except that the reaction time was changed to 0.5 h, and the hydrogen yield was
[0086] Embodiment 24
[0087] The preparation process described in Example 4 was repeated, except that the reaction time was changed to 1 h, and the hydrogen yield was
[0088] Embodiment 25
[0089] The preparation process described in Example 4 was repeated, except that the reaction time was changed to 2 h, and the hydrogen yield was obtained.
[0090] Embodiment 26
[0091] The preparation process described in Example 4 was repeated, except that the reaction time was changed to 3 h, and the hydrogen yield was
[0092] Embodiment 27
[0093] The preparation process described in Example 4 was repeated, except that the reaction time was changed to 4 h, and the hydrogen yield was obtained.
[0094] Embodiment 28
[0095] The preparation process described in Example 5 was repeated, except that the reaction temperature was changed to 250°C, and the hydrogen production was obtained.
[0096] Embodiment 29
[0097] The preparation process described in Example 5 was repeated, except that the reaction temperature was changed to 260°C, and the hydrogen production was obtained.
[0098] Embodiment 30
[0099] The preparation process described in Example 5 was repeated, except that the reaction temperature was changed to 270°C, and the hydrogen production was obtained.
[0100] Embodiment 31
[0101] The preparation process described in Example 5 was repeated, except that the reaction temperature was changed to 280°C, and the hydrogen production was obtained.
[0102] Embodiment 32
[0103] The preparation process described in Example 6 was repeated, except that the solvent water was replaced with methanol, and the hydrogen yield was
[0104] Embodiment 33
[0105] The preparation process described in Example 6 was repeated, except that the solvent water was changed to ethanol, and the hydrogen yield was
[0106] Embodiment 34
[0107] The preparation process described in Example 6 was repeated, except that the solvent water was changed to propanol, and the hydrogen yield was obtained.
[0108] Embodiment 35
[0109] The preparation process described in Example 6 was repeated, except that the solvent water was replaced with ethylene glycol, and the hydrogen yield was
[0110] Embodiment 36
[0111] The preparation process described in Example 6 was repeated, except that the solvent water was replaced with glycerol, and the hydrogen yield was obtained as follows:
[0112] Embodiment 37
[0113] The preparation process described in Example 6 was repeated, except that the polycarbonate powder was replaced with polycarbonate pellets, and the hydrogen production was obtained to be
[0114] Embodiment 38
[0115] The preparation process described in Example 6 was repeated, except that the polycarbonate powder was replaced with a polycarbonate tube, and the hydrogen production was obtained.
[0116] Embodiment 39
[0117] The preparation process described in Example 6 was repeated, except that the polycarbonate powder was replaced with polycarbonate sheets, and the hydrogen production was obtained to be
[0118] Embodiment 40
[0119] The preparation process described in Example 6 was repeated, except that the polycarbonate powder was replaced by optical disk, and the hydrogen production was obtained to be
[0120] Embodiment 41
[0121] The preparation process described in Example 6 was repeated, except that the reaction time was changed to 0.5 h, and the hydrogen yield was obtained.
[0122] Embodiment 42
[0123] The preparation process described in Example 6 was repeated, except that the reaction time was changed to 3 h, and the hydrogen yield was
[0124] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for producing hydrogen using polycarbonate plastic as raw material, characterized in that: The following steps are involved: The raw materials containing polycarbonate plastic, Raney-type catalyst and water are reacted in a sealed pressure container under an inert gas atmosphere to obtain a product containing hydrogen.
2. The method according to claim 1, characterized in that The polycarbonate plastic is selected from at least one of polycarbonate powder, polycarbonate particles, optical discs, polycarbonate tubes, and polycarbonate sheets.
3. The method according to claim 1, characterized in that The Raney-type catalyst is selected from at least one of Raney Ni, Raney Ni-Al, Raney Ni-Mo, Raney Ni-Sn, Raney Ni-Fe, and Raney Ni-Cu.
4. The method according to claim 1, characterized in that: The mass of the Raney-type catalyst is 20-70wt% of the mass of the polycarbonate plastic; Preferably, the mass of the Raney-type catalyst is 50-70 wt % of the mass of the polycarbonate plastic.
5. The method according to claim 1, characterized in that The inert gas atmosphere is selected from at least one of nitrogen, argon and helium.
6. The method according to claim 1, characterized in that The pressure of the inert gas atmosphere is 0.1-7 MPa; Preferably, the pressure of the inert gas atmosphere is 0.1-4 MPa; Preferably, the pressure of the inert gas atmosphere is 0.1-2 MPa.
7. The method according to claim 1, characterized in that The reaction temperature is 250-350°C; Preferably, the reaction temperature is 280-350°C; Preferably, the reaction temperature is 300-350°C.
8. The method according to claim 1, characterized in that The reaction time is 0.05 to 24 hours; Preferably, the reaction time is 0.05 to 10 h; Preferably, the reaction time is 0.5 to 10 h.
9. The method according to claim 1, characterized in that: The Raney-type catalyst includes a Raney-type catalyst which is separated and reused after participating in the reaction.