CN215249587U - Carbon dioxide resourceful treatment system - Google Patents

Carbon dioxide resourceful treatment system Download PDF

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CN215249587U
CN215249587U CN202121043094.2U CN202121043094U CN215249587U CN 215249587 U CN215249587 U CN 215249587U CN 202121043094 U CN202121043094 U CN 202121043094U CN 215249587 U CN215249587 U CN 215249587U
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methane
outlet
hydrogen
raw material
thermal cracking
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毛宗强
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Weichai Power Co Ltd
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Weichai Power Co Ltd
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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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The utility model belongs to the environmental protection field especially relates to a carbon dioxide resourceful treatment system. The utility model provides a system includes: a methane synthesis device, methane separation equipment and a thermal cracking device; the methane synthesis device uses hydrogen and CO2As a reaction raw material, preparing methane by catalysis; the methane separation equipment is used for separating reaction products conveyed by the methane synthesis device to respectively obtain methane, water and unreacted raw material, and a feed inlet of the methane separation equipment is connected with the methane synthesis deviceThe reaction product outlets are connected; the thermal cracking device is used for carrying out catalytic cracking on methane to prepare hydrogen and solid carbon materials, and a feed inlet of the thermal cracking device is connected with a methane outlet of the methane separation equipment. The system provided by the utility model can be used for connecting CO2Conversion to solid carbon material to CO2The carbon dioxide content in the atmospheric environment is reduced fundamentally, and the method has good environmental benefit and economic benefit.

Description

Carbon dioxide resourceful treatment system
Technical Field
The utility model belongs to the environmental protection field especially relates to a carbon dioxide resourceful treatment system.
Background
Currently, 80% of the energy worldwide comes from fossil energy such as coal, oil and natural gas. The use of fossil energy emits a large amount of carbon dioxide, which has been increasingly serious in recent years, and is considered as a "main cause" of climate warming. In the face of increasingly stringent environmental concerns, Carbon Capture and Sequestration (CCS) technology has been operated, which refers to the capture and separation of carbon dioxide from associated emissions combustion sources, for long-term (thousands of years) sequestration delivered to oil and gas fields, oceans, etc., thereby preventing or significantly reducing greenhouse gas emissions and mitigating the effects on the earth's climate. However, the current carbon sealing technology is difficult to realize, the sealing cost is high, the economical efficiency is poor, and the carbon sealing technology is difficult to widely popularize and use.
SUMMERY OF THE UTILITY MODEL
In view of this, the utility model aims to provide a carbon dioxide resourceful treatment system, the utility model provides a system can be with CO2Conversion to solid carbon material to CO2The carbon dioxide content in the atmospheric environment is reduced fundamentally, and the method has good environmental benefit and economic benefit.
The utility model provides a carbon dioxide resourceful treatment system, include:
a methane synthesis unit; the methane synthesis device uses hydrogen and CO2Catalytic preparation of methane as a reaction raw material, on which CO is arranged2An inlet, a hydrogen inlet and a reaction product outlet, wherein the inside of the reaction product outlet is filled with a catalyst;
a methane separation device; the methane separation equipment is used for separating reaction products conveyed by the methane synthesis device to respectively obtain methane, water and unreacted raw material, a feed inlet, a methane outlet, a water outlet and an unreacted raw material outlet are arranged on the methane separation equipment, and the feed inlet of the methane separation equipment is connected with the reaction product outlet of the methane synthesis device;
a thermal cracking unit; the thermal cracking device is used for carrying out catalytic cracking on methane to prepare hydrogen and a solid carbon material, a feed inlet, a hydrogen outlet and a solid carbon outlet are arranged on the thermal cracking device, a catalyst is filled in the thermal cracking device, and the feed inlet of the thermal cracking device is connected with the methane outlet of the methane separation equipment.
Preferably, the unreacted raw material outlet of the methane separation device is connected with the methane synthesis device through a pipeline.
Preferably, the hydrogen outlet of the thermal cracking device is connected with the hydrogen inlet of the methane synthesis device through a pipeline.
Preferably, the device also comprises a water electrolysis hydrogen production device; the water electrolysis hydrogen production device is provided with a water inlet and a hydrogen outlet, and the hydrogen outlet of the water electrolysis hydrogen production device is connected with the hydrogen inlet of the methane synthesis device.
Preferably, the water outlet of the methane separation equipment is connected with the water inlet of the water electrolysis hydrogen production device through a pipeline.
Preferably, the catalyst also comprises CO2A purification device; the CO is2The purification device is used for purifying CO2Removing impurities from the raw material gas to obtain high-purity CO2On which CO is arranged2Raw material gas inlet and high-purity CO2Outlet of said high purity CO2CO of the outlet and the methane synthesis unit2The inlets are connected.
Compared with the prior art, the utility model provides a carbon dioxide resourceful treatment system. The utility model provides a system includes: a methane synthesis unit; the methane synthesis device uses hydrogen and CO2Catalytic preparation of methane as a reaction raw material, on which CO is arranged2An inlet, a hydrogen inlet and a reaction product outlet, wherein the inside of the reaction product outlet is filled with a catalyst; a methane separation device; the methane separation equipment is used for separating reaction products conveyed by the methane synthesis device to respectively obtain methane, water and unreacted raw material, a feed inlet, a methane outlet, a water outlet and an unreacted raw material outlet are arranged on the methane separation equipment, and the feed inlet of the methane separation equipment and the reaction product outlet of the methane synthesis deviceConnecting; a thermal cracking unit; the thermal cracking device is used for carrying out catalytic cracking on methane to prepare hydrogen and a solid carbon material, a feed inlet, a hydrogen outlet and a solid carbon outlet are arranged on the thermal cracking device, a catalyst is filled in the thermal cracking device, and the feed inlet of the thermal cracking device is connected with the methane outlet of the methane separation equipment. CO 22The methane is sequentially subjected to methane synthesis and thermal cracking in the system and finally converted into a solid carbon material, so that not only is CO realized2The resource treatment can be realized, the carbon dioxide content in the atmospheric environment can be reduced fundamentally, and the environmental benefit and the economic benefit are good.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a flow chart of a carbon dioxide recycling treatment system provided by an embodiment of the present invention;
fig. 2 is an SEM image of solid carbon provided by an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.
The utility model provides a carbon dioxide resourceful treatment system, include:
a methane synthesis unit; the methane synthesis device uses hydrogen and CO2Catalytic preparation of methane as a reaction raw material, on which CO is arranged2An inlet, an outlet,A hydrogen inlet and a reaction product outlet, wherein the inside of the hydrogen inlet and the reaction product outlet is filled with a catalyst;
a methane separation device; the methane separation equipment is used for separating reaction products conveyed by the methane synthesis device to respectively obtain methane, water and unreacted raw material, a feed inlet, a methane outlet, a water outlet and an unreacted raw material outlet are arranged on the methane separation equipment, and the feed inlet of the methane separation equipment is connected with the reaction product outlet of the methane synthesis device;
a thermal cracking unit; the thermal cracking device is used for carrying out catalytic cracking on methane to prepare hydrogen and a solid carbon material, a feed inlet, a hydrogen outlet and a solid carbon outlet are arranged on the thermal cracking device, a catalyst is filled in the thermal cracking device, and the feed inlet of the thermal cracking device is connected with the methane outlet of the methane separation equipment.
Referring to fig. 1, fig. 1 is a flow chart of a carbon dioxide recycling treatment system provided by an embodiment of the present invention, wherein 1 is CO2The device comprises a purification device, a water electrolysis hydrogen production device 2, a methane synthesis device 3, a methane separation device 4 and a thermal cracking device 5.
The system provided by the utility model comprises a methane synthesis device 3, a methane separation device 4 and a thermal cracking device 5. Wherein the methane synthesis device 3 uses hydrogen and CO2As a reaction raw material, preparing methane by catalysis; the methane synthesis device 3 is provided with CO2The inlet, the hydrogen inlet and the reaction product outlet are filled with catalyst. In the present invention, the catalyst is preferably a supported nickel-based catalyst, and may be Ni/Al2O3The mass ratio of Ni to the carrier is preferably 5: (2-6), more preferably 5: 4.
In the system provided by the utility model, the methane separation equipment 4 is used for separating the reaction product delivered by the methane synthesis device 3 to respectively obtain methane, water and unreacted raw material; the methane separation equipment 4 is provided with a feed inlet, a methane outlet, a water outlet and an unreacted raw material outlet, and the feed inlet of the methane separation equipment 4 is connected with a reaction product outlet of the methane synthesis device 3. In the present invention, the methane separation apparatus 4 preferably comprises a cyclone separator and a pressure swing adsorption gas arranged in seriesA body separation device; the cyclone separator is used for carrying out gas-liquid two-phase separation on a reaction product conveyed out by the methane synthesis device 3, the gas phase obtained by separation is mixed gas of unreacted raw material and methane, and the liquid phase obtained by separation is water; the pressure swing adsorption gas separation device is used for carrying out secondary separation on the gas phase obtained by the separation of the cyclone separator to respectively obtain unreacted raw materials (hydrogen and CO)2) And methane, the pressure swing adsorption gas separation device preferably consists of 2 adsorption towers arranged in series. In the present invention, it is preferable that the unreacted raw material outlet of the methane separation apparatus 4 is connected to the methane synthesizing device 3 through a pipe for passing unreacted hydrogen and CO2Is conveyed back to the methane synthesis device 3 to continuously participate in the reaction so as to improve the utilization rate of the raw materials.
In the system provided by the utility model, the thermal cracking device 5 is used for carrying out catalytic cracking on methane to prepare hydrogen and solid carbon materials; the thermal cracking device 5 is provided with a feed inlet, a hydrogen outlet and a solid carbon outlet, a catalyst is filled in the thermal cracking device 5, and the feed inlet of the thermal cracking device 5 is connected with the methane outlet of the methane separation equipment 4. In the present invention, the catalyst preferably comprises Ni/Cu/SiO2、Ni/Fe/SiO2And Fe/SiO2One or more of; the Ni/Cu/SiO2The atomic ratio of the medium Ni to the Cu is preferably (5-10): 2, more preferably 8:2, Ni and SiO2The mass ratio is preferably 5: (2-6), more preferably 5:4, SiO as a carrier2The specific surface area of (A) is preferably 30 to 50m2A ratio of 40.6 m/g is more preferable2(ii)/g; the Ni/Fe/SiO2The atomic ratio of the Ni to the Fe is preferably (5-10): 2, more preferably 8:2, Ni and SiO2The mass ratio is preferably 5: (2-6), more preferably 5:4, SiO as a carrier2The specific surface area of (A) is preferably 30 to 50m2A ratio of 40.6 m/g is more preferable2(ii)/g; the Fe/SiO2Middle Fe and SiO2The mass ratio is preferably 5: (2-6), more preferably 5:4, SiO as a carrier2The specific surface area of (A) is preferably 30 to 50m2A ratio of 40.6 m/g is more preferable2(ii) in terms of/g. In the utility model, the hydrogen outlet of the thermal cracking device 5 is connected with the hydrogen inlet of the methane synthesizing device 3The reactors are preferably connected through a pipeline, and the pipeline is used for conveying part or all of the hydrogen obtained by thermal cracking back to the methane synthesis device 3 to continuously participate in the reaction so as to realize the cyclic utilization of the hydrogen.
In the system provided by the utility model, the system preferably further comprises a water electrolysis hydrogen production device 2; the water electrolysis hydrogen production device 2 is used for preparing raw material hydrogen required by methane synthesis, a water inlet and a hydrogen outlet are arranged on the water electrolysis hydrogen production device, and the hydrogen outlet of the water electrolysis hydrogen production device 2 is connected with the hydrogen inlet of the methane synthesis device 3. In the utility model, the water electrolysis hydrogen production device 2 can be specifically an alkaline water electrolyzer; the electrical energy consumed by the operation of the water electrolytic hydrogen production apparatus 2 is preferably provided by electricity generated from renewable energy sources including, but not limited to, one or more of wind energy, solar energy, and hydro energy.
The utility model provides an in the system, if the system is provided with water electrolysis hydrogen plant 2, then link to each other through the pipeline between the water outlet of methane splitter 4 and water electrolysis hydrogen plant 2's the water inlet, the pipeline is arranged in carrying return water electrolysis hydrogen plant 2 with the water that produces in the methane synthesis process to participate in the electrolysis hydrogen production reaction to realize the cyclic utilization of water.
In the system provided by the present invention, the system preferably further comprises CO2A purification device 1; CO 22The purification device 1 is used for the treatment of CO2Removing impurities from the raw material gas to obtain high-purity CO2；CO2The purification device 1 is provided with CO2Raw material gas inlet and high-purity CO2Outlet, CO2High purity CO of the purification plant 12CO of export and methane Synthesis plant 32The inlets are connected. In the utility model, the CO2The raw material gas is CO-containing gas collected from flue gas (such as flue gas discharged from coal-fired power plant and cement plant) or atmosphere2The gas of (2).
The system provided by the utility model uses CO2As a raw material, it undergoes methane synthesis and thermal cracking in the system in order, finally being converted into a solid carbon material. The system can realize CO2The resource disposal of the method also reduces the content of carbon dioxide in the atmospheric environment fundamentallyHas good economic benefit and environmental benefit.
The utility model also provides a carbon dioxide resourceful treatment method, including following step:
a) hydrogen and CO in the presence of a catalyst2Heating for reaction to obtain a mixture containing methane;
b) separating components of the mixture containing methane to respectively obtain methane, water and unreacted raw materials;
c) and carrying out catalytic cracking on the methane to obtain hydrogen and a solid carbon material.
In the method provided by the utility model, hydrogen and CO are firstly used2Methane was synthesized as a starting material. Wherein the hydrogen is preferably obtained by water electrolysis hydrogen production; the equipment adopted by the water electrolysis hydrogen production is preferably the water electrolysis hydrogen production device introduced above; the electrolyte solution for water electrolysis hydrogen production is preferably sodium hydroxide aqueous solution and/or potassium hydroxide aqueous solution; the concentration of the electrolyte solution is preferably 20-40 wt%, and specifically can be 30 wt%; the cathode material for hydrogen production by water electrolysis is preferably Ni or Ni-Mo alloy; the anode material for hydrogen production by water electrolysis is preferably Ni or Ni-Co alloy; the operation pressure of the water electrolysis hydrogen production is preferably less than or equal to 3 MPa; the working temperature of the water electrolysis hydrogen production is preferably 60-80 ℃; the current density of the water electrolysis hydrogen production is preferably 0.2-0.4 mA-cm-2(ii) a The voltage for hydrogen production by water electrolysis is preferably 1.8-2.4V; the power density of the water electrolysis hydrogen production is preferably less than or equal to 1mW cm-2(ii) a H for hydrogen production by water electrolysis2The production rate is preferably 800-1500 m3·h-1Specifically, it may be 1000m3·h-1(ii) a The electrical energy for the water electrolysis hydrogen production is preferably provided by power generation from renewable energy sources including, but not limited to, one or more of wind, solar and hydro energy. In the utility model, the CO2From CO2The raw material gas is obtained after purification and impurity removal, and the CO is2The raw material gas is CO-containing gas collected from flue gas (such as flue gas discharged from coal-fired power plant and cement plant) or atmosphere2The gas of (4); said purification to remove impurities is preferably C as described aboveO2The purification is carried out in a purification device.
In the method provided by the utility model, hydrogen and CO are used2The specific process for synthesizing methane as a raw material comprises the following steps: hydrogen and CO in the presence of a catalyst2Heating for reaction to obtain a mixture containing methane. Wherein the catalyst is preferably a supported nickel-based catalyst, and can be Ni/Al2O3The mass ratio of Ni to the carrier is preferably 5: (2-6), more preferably 5: 4; the hydrogen and CO2Preferably 4: 1; the reaction temperature is preferably 150-300 ℃; the pressure of the reaction is preferably 20-30 bar; the reaction time is preferably 1-5 h, and specifically can be 2 h; the reaction is preferably carried out in a methane synthesis plant as described above.
In the method provided by the utility model, after obtaining the mixture containing methane, it is right the mixture containing methane carries out the component separation, obtains methane, water and unreacted raw materials thing respectively. Wherein, the specific process of the component separation preferably comprises the following steps: firstly, separating gas phase and liquid phase of the mixture containing methane in a cyclone separator to respectively obtain a mixture and water; then continuously separating the mixed gas by adopting a pressure swing adsorption method to respectively obtain unreacted raw materials (hydrogen and CO)2) And methane. Wherein the inlet speed limit of the cyclone separator is preferably 18-25 m/s, and specifically can be 18m/s, 19m/s, 20m/s, 21m/s, 22m/s, 23m/s, 24m/s or 25 m/s; the separation efficiency of the cyclone separator is preferably 85-95%, and specifically can be 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94% or 95%; the resistance loss of the cyclone separator is preferably 800-1500 Pa, and specifically can be 800Pa, 900Pa, 1000Pa, 1100Pa, 1200Pa, 1300Pa, 1400Pa or 1500 Pa; in the process of separating the mixed gas by adopting the pressure swing adsorption method, the adsorption phase time of each pressure swing adsorption cycle period is preferably 2-15 s, more preferably 4-9 s, the emptying and flushing time is preferably 2-15 s, more preferably 4-9 s, and the pressure equalizing process time is preferably 0.5-1.2 s, more preferably 0.8 s. In the present invention, the component separation is preferably the methane separation apparatus described aboveIs carried out in (1). In the utility model, the unreacted raw material obtained by separation is preferably returned to the methane synthesis process for continuous reaction, so as to improve the utilization rate of the raw material; the water obtained by separation is preferably used for the electrolytic production of hydrogen.
In the method provided by the utility model, after methane is obtained by separation, the methane is subjected to catalytic cracking. Wherein the catalyst used for the catalytic cracking preferably comprises Ni/Cu/SiO2、Ni/Fe/SiO2And Fe/SiO2One or more of; the Ni/Cu/SiO2The atomic ratio of the medium Ni to the Cu is preferably (5-10): 2, more preferably 8:2, Ni and SiO2The mass ratio is preferably 5: (2-6), more preferably 5:4, SiO as a carrier2The specific surface area of (A) is preferably 30 to 50m2A ratio of 40.6 m/g is more preferable2(ii)/g; the Ni/Fe/SiO2The atomic ratio of the Ni to the Fe is preferably (5-10): 2, more preferably 8:2, Ni and SiO2The mass ratio is preferably 5: (2-6), more preferably 5:4, SiO as a carrier2The specific surface area of (A) is preferably 30 to 50m2A ratio of 40.6 m/g is more preferable2(ii)/g; the Fe/SiO2Middle Fe and SiO2The mass ratio is preferably 5: (2-6), more preferably 5:4, SiO as a carrier2The specific surface area of (A) is preferably 30 to 50m2A ratio of 40.6 m/g is more preferable2(ii)/g; the temperature of the catalytic cracking is preferably 800-1200 ℃, and specifically can be 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1200 ℃; the pressure of the catalytic cracking is preferably 1-3 bar, and specifically can be 1bar, 1.5bar, 2bar, 2.5bar or 3 bar; the time of the catalytic cracking is preferably 0.5-2 mim, and specifically can be 0.5mim, 1mim, 1.5mim or 2 mim; the catalytic cracking is preferably carried out in a thermal cracking unit as described above. And after the catalytic cracking is finished, obtaining hydrogen and a solid carbon material. Wherein, the hydrogen is preferably totally or partially used as a reaction raw material to return to the methane synthesis process; the solid carbon preferably includes one or more of carbon nanotubes, carbon black and amorphous carbon, and may be carbon nanotubes.
The method provided by the utility model uses CO2As raw material, sequentially undergoes methane synthesis and thermal cracking, and is finally converted intoA solid carbon material. The method can realize CO2The resource treatment also reduces the carbon dioxide content in the atmospheric environment fundamentally, and has good environmental benefit and economic benefit.
For the sake of clarity, the following examples are given in detail.
Example 1
The resource treatment of carbon dioxide is carried out in the system shown in figure 1, the products are nano carbon and hydrogen, and the concrete steps are as follows:
1) existing sources of carbon dioxide emissions (carbon sources), e.g. cement plant/coal plant exhaust or atmospheric CO2As raw material gas, by CO2 The purifying device 1 purifies and removes impurities to obtain high-purity CO2；
2) Hydrogen is produced by electrolysis by utilizing the water electrolysis hydrogen production device 2; wherein the water electrolysis hydrogen production device 2 is specifically an alkaline water electrolysis cell, the electrolyte solution is 30 wt% of potassium hydroxide water solution, the cathode material is Ni or Ni-Mo alloy, the anode material is Ni or Ni-Co alloy, the operating pressure is less than or equal to 3MPa, the working temperature is 60-80 ℃, and the current density is 0.2-0.4 mA-cm-2The voltage is 1.8-2.4V, and the power density is less than or equal to 1mW cm-2，H2The production rate is more than or equal to 1000m3·h-1The electric energy required by electrolysis is provided by renewable energy sources (wind energy, solar energy, water energy and the like);
3) the high-purity CO prepared in the step 1) is used2And the hydrogen prepared in step 2) is mixed with the hydrogen in a molar ratio of: CO 22Conveying the obtained product to a methane synthesis device 3 for reaction at a ratio of 4: 1; wherein the catalyst filled in the methane synthesis device 3 is a supported nickel-based catalyst (Ni/Al)2O3Ni and Al2O3The mass ratio is 5:4), the reaction temperature is controlled at 280 ℃, the reaction pressure is controlled at 25bar, and the retention time of the raw material gas in the methane synthesis device is controlled at 2 h;
4) discharging the mixture containing methane obtained by the reaction in the step 3) from a reaction product outlet of the methane synthesis device 3, and conveying the mixture to a methane separation device 4 for component separation to obtain methane (gas state), water (liquid state) and unreacted raw materials (gas state); wherein, the methane separation deviceThe device 4 consists of a cyclone separator and a pressure swing adsorption gas separation device which are arranged in series, the pressure swing adsorption gas separation device consists of 2 adsorption towers which are arranged in series, the height of each adsorption tower is 950mm, the diameter of each adsorption tower is 168mm, the adsorption towers are filled with active carbon and carbon molecular sieve mixed adsorbents, and the effective filling volume of the adsorbents in each adsorption tower is 1.23 multiplied by 10-3m3(ii) a When equipment is operated, the speed limit of an inlet of the cyclone separator is 21m/s, the separation efficiency is 90%, the resistance loss is 1000Pa, the time of an adsorption stage of each pressure swing adsorption cycle period of the pressure swing adsorption gas separation device is 4-9 s, the time of emptying and flushing is 4-9 s, and the time of a pressure equalizing process is 0.8 s; during the operation of the equipment, the mixture containing methane is firstly separated into gas-liquid two phases in the cyclone separator, the liquid phase is water, the gas phase is the mixed gas of the unreacted raw material and methane, and then the mixed gas is continuously separated in the pressure swing adsorption gas separation device to respectively obtain the unreacted raw materials (hydrogen and CO)2) And methane; the water is used as a hydrogen production raw material and is conveyed to a water electrolysis hydrogen production device 2, the unreacted raw material returns to a methane synthesis device 3 for circular reaction, and the methane is treated by a downstream process;
5) conveying the methane obtained in the step 4) to a thermal cracking device 5 for catalytic cracking; wherein the catalyst filled in the thermal cracking device 5 is Ni/Cu/SiO2(Ni/Cu atomic ratio 8:2, Ni/SiO)2The mass ratio is 5:4, and the carrier is SiO2Has a specific surface area of 40.6m2The temperature of the catalytic cracking is controlled to be 1000 ℃, the pressure of the catalytic cracking is controlled to be 1.5bar, and the residence time of the methane in the thermal cracking device is controlled to be about 1 mim; after catalytic cracking, methane is directly cracked to generate a solid carbon material and hydrogen, and part of the hydrogen is used as a reaction raw material and returns to the methane synthesis device 3 for circular reaction.
The hydrogen obtained in step 4) of this example was subjected to composition analysis, and the results were: the purity is 99 percent; the impurity components are CO and CO2And each accounts for about 0.5%.
The solid carbon material obtained in step 4) of this example was analyzed, and the results were: bulk density 1.7g/cm3Young's modulus 2.7GPa, bendThe bending strength is 173.7MPa, and the specific surface area is about 120m2G, pore volume of about 310cm3(iv)/g, micro-topography (SEM) as shown in FIG. 2; as can be seen from FIG. 2, the product contains a large amount of carbon nanotubes, a small amount of carbon nanotubes are entangled, a part of particles are attached to the walls of the carbon nanotubes, and the diameter of the carbon nanotubes is about 40-50 nm.
Example 2
The resource treatment of carbon dioxide is carried out in the system shown in figure 1, and the products are carbon black and hydrogen for tires, and the concrete steps are as follows:
1) existing sources of carbon dioxide emissions (carbon sources), e.g. cement plant/coal plant exhaust or atmospheric CO2As raw material gas, by CO2 The purifying device 1 purifies and removes impurities to obtain high-purity CO2；
2) Hydrogen is produced by electrolysis by utilizing the water electrolysis hydrogen production device 2; wherein the water electrolysis hydrogen production device 2 is specifically an alkaline water electrolysis cell, the electrolyte solution is 30 wt% of potassium hydroxide water solution, the cathode material is Ni or Ni-Mo alloy, the anode material is Ni or Ni-Co alloy, the operating pressure is less than or equal to 3MPa, the working temperature is 60-80 ℃, and the current density is 0.2-0.4 mA-cm-2The voltage is 1.8-2.4V, and the power density is less than or equal to 1mW cm-2，H2The production rate is more than or equal to 1000m3·h-1The electric energy required by electrolysis is provided by renewable energy sources (wind energy, solar energy, water energy and the like);
3) the high-purity CO prepared in the step 1) is used2And the hydrogen prepared in step 2) is mixed with the hydrogen in a molar ratio of: CO 22Conveying the obtained product to a methane synthesis device 3 for reaction at a ratio of 4: 1; wherein the catalyst filled in the methane synthesis device 3 is a supported nickel-based catalyst (Ni/Al)2O3Ni and Al2O3The mass ratio is 5:4), the reaction temperature is controlled at 280 ℃, the reaction pressure is controlled at 25bar, and the retention time of the raw material gas in the methane synthesis device is controlled at 2 h;
4) discharging the mixture containing methane obtained by the reaction in the step 3) from a reaction product outlet of the methane synthesis device 3, and conveying the mixture to a methane separation device 4 for component separation to obtain methane (gas state), water (liquid state) and unreacted raw materials (gas state); wherein, methaneThe separation equipment 4 consists of a cyclone separator and a pressure swing adsorption gas separation device which are arranged in series, the pressure swing adsorption gas separation device consists of 2 adsorption towers which are arranged in series, the tower heights are 950mm, the tower diameters are 168mm, the adsorption towers are filled with active carbon and carbon molecular sieve mixed adsorbents, and the effective filling volume of the adsorbents in each adsorption tower is 1.23 multiplied by 10-3m3(ii) a When equipment is operated, the speed limit of an inlet of the cyclone separator is 22m/s, the separation efficiency is 89%, the resistance loss is 1200Pa, the time of an adsorption stage of each pressure swing adsorption cycle period of the pressure swing adsorption gas separation device is 4-9 s, the time of emptying and flushing is 4-9 s, and the time of a pressure equalizing process is 0.8 s; during the operation of the equipment, the mixture containing methane is firstly separated into gas-liquid two phases in the cyclone separator, the liquid phase is water, the gas phase is the mixed gas of the unreacted raw material and methane, and then the mixed gas is continuously separated in the pressure swing adsorption gas separation device to respectively obtain the unreacted raw materials (hydrogen and CO)2) And methane; the water is used as a hydrogen production raw material and is conveyed to a water electrolysis hydrogen production device 2, the unreacted raw material returns to a methane synthesis device 3 for circular reaction, and the methane is treated by a downstream process;
5) conveying the methane obtained in the step 4) to a thermal cracking device 5 for catalytic cracking; wherein the catalyst filled in the thermal cracking device 5 is Ni/Fe/SiO2(Ni/Fe atomic ratio 8:2, Ni/SiO)2The mass ratio is 5:4, and the carrier is SiO2Has a specific surface area of 40.6m2/g), the catalytic cracking temperature is controlled at 950 ℃, the catalytic cracking pressure is controlled at 1.5bar, and the residence time of methane in the thermal cracking device is controlled at about 2 mm; after catalytic cracking, methane is directly cracked to generate a solid carbon material and hydrogen, and part of the hydrogen is used as a reaction raw material and returns to the methane synthesis device 3 for circular reaction.
The hydrogen obtained in step 4) of this example was subjected to composition analysis, and the results were: the purity is 99 percent; the impurity components are CO and CO2And each accounts for about 0.5%.
The solid carbon material obtained in the step 4) of the embodiment is detected and analyzed, and the parameters such as iodine absorption value, DBF absorption value and coloring strength all accord with the national standard of GB 3778-2003 carbon black for rubber.
Example 3
The resource treatment of carbon dioxide is carried out in the system shown in figure 1, the products are carbon black and hydrogen for a zinc-manganese dry battery, and the concrete steps are as follows:
1) existing sources of carbon dioxide emissions (carbon sources), e.g. cement plant/coal plant exhaust or atmospheric CO2As raw material gas, by CO2 The purifying device 1 purifies and removes impurities to obtain high-purity CO2；
2) Hydrogen is produced by electrolysis by utilizing the water electrolysis hydrogen production device 2; wherein the water electrolysis hydrogen production device 2 is specifically an alkaline water electrolysis cell, the electrolyte solution is 30 wt% of potassium hydroxide water solution, the cathode material is Ni or Ni-Mo alloy, the anode material is Ni or Ni-Co alloy, the operating pressure is less than or equal to 3MPa, the working temperature is 60-80 ℃, and the current density is 0.2-0.4 mA-cm-2The voltage is 1.8-2.4V, and the power density is less than or equal to 1mW cm-2，H2The production rate is more than or equal to 1000m3·h-1The electric energy required by electrolysis is provided by renewable energy sources (wind energy, solar energy, water energy and the like);
3) the high-purity CO prepared in the step 1) is used2And the hydrogen prepared in step 2) is mixed with the hydrogen in a molar ratio of: CO 22Conveying the obtained product to a methane synthesis device 3 for reaction at a ratio of 4: 1; wherein the catalyst filled in the methane synthesis device 3 is a supported nickel-based catalyst (Ni/Al)2O3Ni and Al2O3The mass ratio is 5:4), the reaction temperature is controlled at 280 ℃, the reaction pressure is controlled at 25bar, and the retention time of the raw material gas in the methane synthesis device is controlled at 2 h;
4) discharging the mixture containing methane obtained by the reaction in the step 3) from a reaction product outlet of the methane synthesis device 3, and conveying the mixture to a methane separation device 4 for component separation to obtain methane (gas state), water (liquid state) and unreacted raw materials (gas state); wherein, the methane separation equipment 4 consists of a cyclone separator and a pressure swing adsorption gas separation device which are arranged in series, the pressure swing adsorption gas separation device consists of 2 adsorption towers which are arranged in series, the tower heights are 950mm, the tower diameters are 168mm, and the adsorption towers are filled with active carbon and carbonMolecular sieve mixed adsorbent, effective packing volume of adsorbent in each adsorption tower is 1.23X 10-3m3(ii) a When equipment is operated, the speed limit of an inlet of the cyclone separator is 20m/s, the separation efficiency is 91%, the resistance loss is 1100Pa, the time of an adsorption stage of each pressure swing adsorption cycle period of the pressure swing adsorption gas separation device is 4-9 s, the time of emptying and flushing is 4-9 s, and the time of a pressure equalizing process is 0.8 s; during the operation of the equipment, the mixture containing methane is firstly separated into gas-liquid two phases in the cyclone separator, the liquid phase is water, the gas phase is the mixed gas of the unreacted raw material and methane, and then the mixed gas is continuously separated in the pressure swing adsorption gas separation device to respectively obtain the unreacted raw materials (hydrogen and CO)2) And methane; the water is used as a hydrogen production raw material and is conveyed to a water electrolysis hydrogen production device 2, the unreacted raw material returns to a methane synthesis device 3 for circular reaction, and the methane is treated by a downstream process;
5) conveying the methane obtained in the step 4) to a thermal cracking device 5 for catalytic cracking; wherein the catalyst filled in the thermal cracking device 5 is Fe/SiO2(Fe/SiO2The mass ratio is 5:4, and the carrier is SiO2Has a specific surface area of 40.6m2The temperature of catalytic cracking is controlled to be 850 ℃, the pressure of catalytic cracking is controlled to be 2.5bar, and the residence time of methane in a thermal cracking device is controlled to be about 2 mim; after catalytic cracking, methane is directly cracked to generate a solid carbon material and hydrogen, and part of the hydrogen is used as a reaction raw material and returns to the methane synthesis device 3 for circular reaction.
The hydrogen obtained in step 4) of this example was subjected to composition analysis, and the results were: the purity is 98 percent; the impurity components are CO and CO2Each accounting for about 1%.
The solid carbon material obtained in step 4) of this example was analyzed, and the results were: the particle size is 35-45 mu m, the water content is less than or equal to 0.4 wt%, the specific resistance is less than or equal to 0.4k omega cm, the liquid absorption amount is 3.5-4.4 ml/g, and the apparent specific gravity is 12-16 ml/g. Therefore, each index of the carbon black meets the use requirement of the carbon black for the zinc-manganese dry battery.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A carbon dioxide resourceful treatment system, comprising:
a methane synthesis unit; the methane synthesis device uses hydrogen and CO2Catalytic preparation of methane as a reaction raw material, on which CO is arranged2An inlet, a hydrogen inlet and a reaction product outlet, wherein the inside of the reaction product outlet is filled with a catalyst;
a methane separation device; the methane separation equipment is used for separating reaction products conveyed by the methane synthesis device to respectively obtain methane, water and unreacted raw material, a feed inlet, a methane outlet, a water outlet and an unreacted raw material outlet are arranged on the methane separation equipment, and the feed inlet of the methane separation equipment is connected with the reaction product outlet of the methane synthesis device;
a thermal cracking unit; the thermal cracking device is used for carrying out catalytic cracking on methane to prepare hydrogen and a solid carbon material, a feed inlet, a hydrogen outlet and a solid carbon outlet are arranged on the thermal cracking device, a catalyst is filled in the thermal cracking device, and the feed inlet of the thermal cracking device is connected with the methane outlet of the methane separation equipment.
2. The carbon dioxide recycling system according to claim 1, wherein the unreacted raw material outlet of the methane separation device is connected to the methane synthesis apparatus through a pipeline.
3. The carbon dioxide recycling system as set forth in claim 1, wherein the hydrogen outlet of the thermal cracking device is connected to the hydrogen inlet of the methane synthesis device via a pipeline.
4. The carbon dioxide resourceful disposal system according to claim 1, further comprising a water electrolysis hydrogen production apparatus; the water electrolysis hydrogen production device is provided with a water inlet and a hydrogen outlet, and the hydrogen outlet of the water electrolysis hydrogen production device is connected with the hydrogen inlet of the methane synthesis device.
5. The carbon dioxide resource disposal system as claimed in claim 4, wherein the water outlet of the methane separation device is connected with the water inlet of the water electrolysis hydrogen production device through a pipeline.
6. The carbon dioxide resource disposal system according to claim 1, further comprising CO2A purification device; the CO is2The purification device is used for purifying CO2Removing impurities from the raw material gas to obtain high-purity CO2On which CO is arranged2Raw material gas inlet and high-purity CO2Outlet of said high purity CO2CO of the outlet and the methane synthesis unit2The inlets are connected.
CN202121043094.2U 2021-05-14 2021-05-14 Carbon dioxide resourceful treatment system Active CN215249587U (en)

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