CN113070012B - Reaction device and method for generating methanol by using carbon dioxide and hydrogen - Google Patents
Reaction device and method for generating methanol by using carbon dioxide and hydrogen Download PDFInfo
- Publication number
- CN113070012B CN113070012B CN202110290081.3A CN202110290081A CN113070012B CN 113070012 B CN113070012 B CN 113070012B CN 202110290081 A CN202110290081 A CN 202110290081A CN 113070012 B CN113070012 B CN 113070012B
- Authority
- CN
- China
- Prior art keywords
- discharge area
- reaction
- area
- methanol
- air inlet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention provides a reaction device and a method for generating methanol by using carbon dioxide and hydrogen, belonging to the technical field of chemical synthesis. The reaction device is divided into a first discharge area (4) and a second discharge area (5), because the outer surface of the first discharge area (4) is provided with a metal net (10), the first discharge area (4) becomes a high-temperature discharge area under the electrifying condition of the air inlet pipe (7), and carbon dioxide is converted into carbon monoxide under the high-temperature discharge condition and the action of a first catalyst and reacts with hydrogen to generate a small amount of methanol; because the outer surface of the second discharge area (5) is provided with the cooling device (12), the second discharge area (5) becomes a low-temperature discharge area under the condition that the air inlet pipe (7) is electrified, and under the low-temperature discharge condition and the action of the second catalyst, carbon monoxide, unreacted carbon dioxide and hydrogen generate a large amount of methanol in the second discharge area (5).
Description
Technical Field
The invention relates to the technical field of plasma chemical synthesis, in particular to a reaction device and a method for generating methanol by using carbon dioxide and hydrogen.
Background
With the rapid development of modern industry, CO 2 The concentration rise has caused the consequences of global climate abnormality and grain yield reduction. Therefore, the emission reduction of carbon dioxide becomes a technical problem to be solved urgently. Among them, the conversion of carbon dioxide to produce fuels and chemicals is the most feasible strategy for realizing emission reduction and sustainable utilization of carbon resourcesBut not shown. The reaction process of preparing methanol by catalyzing direct hydrogenation of carbon dioxide can reduce carbon emission and simultaneously generate clean energy, so the method is widely concerned by people.
However, the reaction conditions for preparing methanol by directly hydrogenating catalytic carbon dioxide are severe, for example, the industrial hydrogenation reforming reaction of carbon dioxide needs to be heated to more than 200 ℃ and pressurized to more than 3MPa under the action of a catalyst. The reaction conditions of high temperature and high pressure not only limit the large-scale production, but also bring about the waste of additional energy.
Dielectric barrier discharge is one type of plasma catalysis. Dielectric barrier discharge, also called silent discharge, is a gas discharge with an insulating dielectric inserted into the discharge space. When a sufficiently high ac voltage is applied across the electrodes, the gas between the electrodes breaks down to form a more uniform and stable discharge in appearance, which is actually composed of a large number of fine, fast pulse discharge channels, i.e., microdischarge channels. It belongs to non-thermal equilibrium discharge under high pressure. The insertion of a dielectric between the electrodes prevents the formation of a partial spark or arc discharge in the discharge space, thereby enabling the formation of a stable gas discharge at atmospheric pressure. Dielectric barrier discharge can be used to convert carbon dioxide to methanol at near ambient temperature and pressure, but carbon dioxide conversion and methanol selectivity are not high. Current catalysis of CO using plasma alone 2 The highest carbon dioxide conversion rate of the prepared methanol is 8 percent, and the highest selectivity of the methanol is less than 1 percent.
Disclosure of Invention
In view of the above, the present invention is directed to a reaction apparatus and a method for generating methanol using carbon dioxide and hydrogen, wherein the apparatus provided by the present invention has a simple structure, and can effectively improve the conversion rate of carbon dioxide and the selectivity of methanol.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a reaction device for generating methanol by using carbon dioxide and hydrogen, which comprises an insulating tube 1, wherein the top of the insulating tube 1 is provided with an air inlet 2, and the bottom of the insulating tube 1 is provided with an air outlet 3; the insulating tube 1 is divided into a first discharge area 4 and a second discharge area 5 from top to bottom, and the volume ratio of the first discharge area 4 to the second discharge area 5 is 3; the first discharge area 4 and the second discharge area 5 are separated by a first screen 6; a first catalyst is placed on the first screen plate 6;
the air inlet pipe 7 penetrates through the upper wall of the insulating pipe 1 and extends to the bottom of the insulating pipe 1, and the air inlet pipe 7 is coaxial with the insulating pipe 1; the air inlet pipe 7 is provided with a first exhaust hole 8 and a second exhaust hole 9, the first exhaust hole 8 is located in the first discharge area 4, and the second exhaust hole 9 is located in the second discharge area 5; the air inlet pipe 7 is made of metal;
the metal net 10 is positioned on the outer surface of the first discharge area 4 of the insulating tube 1, and the metal net 10 is connected with the grounding device 11;
the cooling device 12 is positioned on the outer surface of the second discharge area 5 of the insulating tube 1;
and the second screen plate 13 is positioned at the bottom of the second discharge area 5, and a second catalyst is placed on the second screen plate.
Preferably, the opening area of the first exhaust hole 8 is 60-70% of the cross-sectional area of the air inlet pipe 7; the opening area of the second exhaust hole 9 is 30-40% of the cross section area of the air inlet pipe 7.
Preferably, the material of the air inlet pipe 7 is 304 stainless steel or 316 stainless steel.
Preferably, the coverage area of the metal mesh 10 is 30 to 35 percent of the outer surface area of the insulating tube 1.
Preferably, the cooling device 12 is a glass tube heat exchanger, and a heat exchange medium of the glass tube heat exchanger is water; the glass tube heat exchanger is provided with a water inlet 14 and a water outlet 15; the coverage area of the glass tube heat exchanger is 30-35% of the outer surface area of the insulating tube 1.
Preferably, the first catalyst is Cu @ Al 2 O 3 The second catalyst is Cu/Zn @ Al 2 O 3 。
The invention provides a method for generating methanol by using carbon dioxide and hydrogen by using the reaction device, which comprises the following steps:
(1) Introducing H into the air inlet pipe 7 2 Introducing CO into the gas inlet 2 2 The air inlet pipe 7 is electrified, and the first exhaust hole 8 is exhaustedH of (A) 2 With CO 2 Carrying out pre-reaction in the first discharge area 4 to obtain pre-reaction produced gas, wherein the pre-reaction produced gas comprises CO and methanol;
(2) The pre-reaction generates gas and unreacted CO 2 Enters a second discharge area 5, and under the action of a temperature reducing device 12, CO and CO are generated 2 H discharged from the second exhaust hole 9 2 Reforming reaction is carried out to obtain methanol.
Preferably, said H 2 With CO 2 The flow ratio of (1) is 3-4.
Preferably, the frequency of the power supply at the time of energization is 7 to 12kHz, the voltage is 5 to 10kV, and the discharge power is 12 to 32W.
Preferably, the temperature controlled by the cooling device 12 is 5-30 ℃.
The invention provides a reaction device for generating methanol by using carbon dioxide and hydrogen, which comprises an insulating tube 1, an air inlet pipe 7 penetrating through the upper wall of the insulating tube 1 and extending to the bottom of the insulating tube 1, a metal net 10 positioned on the outer surface of a first discharge area 4 of the insulating tube 1, a cooling device 12 positioned on the outer surface of a second discharge area 5 of the insulating tube 1, a first mesh plate 6 for containing a first catalyst and a second mesh plate for containing a second catalyst. According to the invention, the reaction device is divided into a first discharge area 4 and a second discharge area 5, as the metal mesh 10 is arranged on the outer surface of the first discharge area 4, under the condition that the air inlet pipe 7 is electrified, the air inlet pipe 7 is a high-voltage electrode, and the metal mesh 10 connected with the grounding device forms a grounding electrode, the first discharge area 4 becomes a high-temperature discharge area, under the high-temperature discharge condition and the action of a first catalyst, carbon dioxide is converted into carbon monoxide, and the carbon monoxide reacts with hydrogen to generate a small amount of methanol; because the outer surface of the second discharge area 5 is provided with the cooling device 12, the second discharge area 5 becomes a low-temperature discharge area under the condition that the air inlet pipe 7 is electrified, and under the low-temperature discharge condition and the action of the second catalyst, carbon monoxide, unreacted carbon dioxide and hydrogen generate a large amount of methanol in the second discharge area 5. The reaction device is divided into the first discharge area 4 and the second discharge area 5, and the catalytic reforming reaction can be divided into two processes, so that the conversion rate of carbon dioxide and the selectivity of methanol are improved. The device can combine the discharge plasma catalysis with the catalyst catalysis, thereby further improving the carbon dioxide conversion rate and the methanol selectivity. The results of the examples show that the conversion rate of carbon dioxide obtained by the device provided by the invention is 38.65-51.3%, and the selectivity of methanol is 71.3-77.6%.
Meanwhile, the device provided by the invention has a simple structure, can realize the preparation of methanol by reforming carbon dioxide to prepare hydrogen without additional heating and pressurizing devices, and can save resources and reduce production cost.
Drawings
FIG. 1 is a schematic view showing the structure of a reaction apparatus of the present invention, wherein 1-an insulating tube, 2-a gas inlet, 3-an air outlet, 4-a first discharge area, 5-a second discharge area, 6-a first screen plate, 7-an air inlet pipe, 8-a first exhaust hole, 9-a second exhaust hole, 10-a metal net, 11-a grounding device, 12-a cooling device, 13-a second screen plate, 14-a water inlet and 15-a water outlet;
FIG. 2 is a schematic size diagram of a reaction apparatus according to the present invention.
Detailed Description
The invention provides a reaction device for generating methanol by using carbon dioxide and hydrogen, which comprises an insulating tube 1, wherein the top of the insulating tube 1 is provided with an air inlet 2, and the bottom of the insulating tube 1 is provided with an air outlet 3; the insulating tube 1 is divided into a first discharge area 4 and a second discharge area 5 from top to bottom, and the volume ratio of the first discharge area 4 to the second discharge area 5 is 1; the first discharge area 4 and the second discharge area 5 are separated by a first screen 6; a first catalyst is placed on the first screen plate 6;
the air inlet pipe 7 penetrates through the upper wall of the insulating pipe 1 and extends to the bottom of the insulating pipe 1, and the air inlet pipe 7 is coaxial with the insulating pipe 1; the air inlet pipe 7 is provided with a first exhaust hole 8 and a second exhaust hole 9, the first exhaust hole 8 is located in the first discharge area 4, and the second exhaust hole 9 is located in the second discharge area 5; the air inlet pipe 7 is made of metal;
the metal net 10 is positioned on the outer surface of the first discharge area 4 of the insulating tube 1, and the metal net 10 is connected with the grounding device 11;
the cooling device 12 is positioned on the outer surface of the second discharge area 5 of the insulating tube 1;
and the second screen plate is positioned at the bottom of the second discharge area 5, and a second catalyst is placed on the second screen plate.
The reaction apparatus for generating methanol using carbon dioxide and hydrogen provided by the present invention comprises an insulating tube 1. In the present invention, the material of the insulating tube 1 is preferably a quartz glass tube; the invention has no special requirements on the size specification of the insulating tube 1, and can be designed correspondingly according to the actual situation. In the invention, the top of the insulating tube 1 is provided with an air inlet 2, and the air inlet 2 is used for introducing CO 2 (ii) a And the bottom of the insulating tube 1 is provided with an air outlet 3 for discharging final produced gas.
In the present invention, the insulating tube 1 is divided into a first arrester region 4 and a second arrester region 5 from top to bottom, and the volume ratio of the first arrester region 4 to the second arrester region 5 is 1. In the invention, the first discharge area 4 and the second discharge area 5 are separated by a first screen 6; the first screen 6 is provided with a first catalyst.
In the invention, the first mesh plate 6 is horizontally fixed in the insulating tube 1, and the material of the first mesh plate 6 is preferably metal, and more preferably stainless steel; in the present invention, the pore size of the first mesh plate 6 is preferably 40 to 60 mesh, and more preferably 50 mesh. In the present invention, the first steel sheet is used to contain a first catalyst.
In the present invention, the first catalyst is preferably Cu @ Al 2 O 3 Catalyst, said Cu @ Al 2 O 3 The catalyst is Al 2 O 3 A Cu-supported catalyst, the loading of Cu in the first catalyst preferably being 8%.
The reaction device for generating methanol by using carbon dioxide and hydrogen comprises an air inlet pipe 7 which penetrates through the upper wall of an insulating pipe 1 and extends to the bottom of the insulating pipe 1, wherein the air inlet pipe 7 is coaxial with the insulating pipe 1; intake pipe 7 is equipped with first exhaust hole 8 and second exhaust hole 9, first exhaust hole 8 is located first discharge area 4, second exhaust hole 9 is located second discharge area 5. In the present invention, the material of the intake pipe 7 is metal, and more preferably 304 stainless steel or 316 stainless steel. The invention has no special requirement on the inner diameter of the air inlet pipe 7, and the air inlet pipe 7 is designed correspondingly according to the actual gas flow, and as a specific embodiment of the invention, the inner diameter of the air inlet pipe 7 is preferably 2mm.
In the present invention, the number of the first exhaust holes 8 is preferably plural; when the number of the first exhaust holes 8 is plural, the total opening area of the first exhaust holes 8 is preferably 60 to 70%, and more preferably 64 to 68% of the cross-sectional area of the intake pipe 7; in the present invention, the number of the first exhaust holes 8 is preferably plural; when the number of the first exhaust holes 8 is plural, the total open area of the first exhaust holes 8 is preferably 30 to 40%, more preferably 32 to 36% of the cross-sectional area of the intake pipe 7. The invention can lead H to be discharged through the arrangement of the first exhaust hole 8 and the second exhaust hole 9 2 Respectively to the first discharge area 4 and the second discharge area 5. Furthermore, the invention can control the H in the first discharge area 4 and the second discharge area 5 by controlling the opening area of the first exhaust hole 8 and the second exhaust hole 9 2 The flow rate of (c).
The reaction device for generating methanol by using carbon dioxide and hydrogen comprises a metal net 10 positioned on the outer surface of a first discharge area 4 of an insulating tube 1. In the invention, under the condition that the air inlet pipe 7 is electrified, the air inlet pipe 7, the insulating pipe 1 and the metal mesh 10 can form a high-temperature discharge area, and plasma is generated in the discharge process. In the present invention, the metal mesh 10 is preferably made of stainless steel; the mesh aperture of the metal net 10 is preferably 40 to 60 mesh, and more preferably 50 mesh. In the present invention, the coverage area of the metal mesh 10 is 30 to 35%, preferably 32 to 34% of the outer surface area of the insulating tube 1.
In the present invention, the metal mesh 10 is connected to a grounding device 11; in the present invention, the grounding device 11 is preferably a metal rod, and the metal rod is connected with a grounding wire; as an embodiment of the invention, the metal rod is positioned on the surface of the insulating tube 1 and fixed between the metal mesh 10 and the cooling device 12.
The reaction device for generating methanol by using carbon dioxide and hydrogen comprises a cooling device 12 positioned on the outer surface of the second discharge area 5 of the insulating tube 1. In the invention, the cooling device 12 is preferably a glass tube heat exchanger, and water is introduced into the glass tube heat exchanger; the glass tube heat exchanger is provided with a water inlet 14 and a water outlet 15; the coverage area of the glass tube heat exchanger is preferably 30 to 35%, more preferably 32 to 34% of the outer surface area of the insulating tube 1.
The reaction device for generating the methanol by utilizing the carbon dioxide and the hydrogen comprises a second screen plate 13 positioned at the bottom of the second discharge area 5, and a second catalyst is placed on the second screen plate. In the invention, the second mesh plate is horizontally fixed in the insulating tube 1, and the material of the second mesh plate 13 is preferably metal, and more preferably stainless steel; in the present invention, the pore size of the second mesh plate 13 is preferably 40 to 60 mesh, and more preferably 50 mesh. In the present invention, the second mesh plate 13 is used to hold a second catalyst.
In the present invention, the second catalyst is preferably Cu/Zn @ Al 2 O 3 The Cu/Zn @ Al 2 O 3 The catalyst is Al 2 O 3 A catalyst supporting an active ingredient, the active ingredient being Cu and/or Zn; the loading amount of the active ingredient in the second catalyst is preferably 10%.
The device can combine the discharge plasma catalysis with the catalyst catalysis, thereby further improving the carbon dioxide conversion rate and the methanol selectivity. The present invention uses a Cu-based catalyst as the first catalyst because the Cu-based catalyst can generate partially oxidized Cu δ O particles in plasma to make CO 2 CO can form intermediate products with carboxylate and formate structures, and the intermediate products are further hydrogenated to generate methanol; the invention uses Cu/Zn-based catalyst as the second catalyst, the Zn component enhances the adsorption energy of Cu to key intermediate products and utilizes H 2 Protecting the generated methanol; the invention selects Al 2 O 3 As a carrier, the carrier can enhance the discharge effect in a discharge region and further improve the selectivity of methanol. Therefore, the device provided by the invention can perfectly realize high CO 2 Conversion and methanol selectivity.
In the present invention, a schematic configuration of the reaction apparatus for producing methanol using carbon dioxide and hydrogen is shown in fig. 1.
As an embodiment of the present invention, the size of the reaction apparatus for producing methanol using carbon dioxide and hydrogen is shown in FIG. 2, and the unit in FIG. 2 is mm.
The invention provides a method for generating methanol by utilizing carbon dioxide and hydrogen based on the reaction device, which comprises the following steps:
(1) Introducing H into the air inlet pipe 7 2 Introducing CO into the gas inlet 2 2 H discharged from the first exhaust port 8 by energizing the intake pipe 7 2 With CO 2 Carrying out pre-reaction in the first discharge area 4 to obtain pre-reaction produced gas, wherein the pre-reaction produced gas comprises CO and methanol;
(2) Gas production by pre-reaction and unreacted CO 2 Enters a second discharge area 5, and under the action of a temperature reducing device 12, CO and CO are generated 2 H discharged from the second exhaust hole 9 2 Reforming reaction is carried out to obtain methanol.
In the present invention, before the energization, it is preferable to purge the insulating tube 1 to discharge the air in the insulating tube 1. In the present invention, the gas washing is preferably performed by: continuously introducing H 2 And CO 2 5min。
H is introduced into an air inlet pipe 7 by the invention 2 Introducing CO into the gas inlet 2 2 H discharged from the first exhaust port 8 by energizing the intake pipe 7 2 With CO 2 And carrying out pre-reaction in the first discharge area 4 to obtain pre-reaction produced gas, wherein the pre-reaction produced gas comprises CO and methanol. In the present invention, said H 2 With CO 2 The flow ratio of (3) to (4), preferably 3.2 to 3.5. In the present invention, said H 2 The introducing rate of (A) is preferably 300-600 sccm, more preferably 400-500 sccm; the CO is 2 The flow rate of (A) is preferably 100 to 150sccm, more preferably 120sccm.
In the present invention, the frequency of the power supply at the time of energization is preferably 7 to 12kHz, more preferably 8 to 10kHz; the voltage is preferably 5 to 10kV, more preferably 6 to 8kV; the discharge power is preferably 12 to 32W, more preferably 20 to 30W.
In the present invention, the temperature controlled by the cooling device 12 is preferably 5 to 30 ℃, and more preferably 10 to 20 ℃. When the cooling device 12 is a glass tube heat exchanger, the flow rate of water in the heat exchanger is 80-100 mL/min, and more preferably 90mL/min.
The reaction apparatus and method for producing methanol using carbon dioxide and hydrogen according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Methanol was produced using carbon dioxide and hydrogen using the reaction apparatus shown in fig. 1, as follows:
(1) Introducing carbon dioxide and hydrogen into the insulating pipe 1 from an air inlet 2 and an air inlet pipe 7 respectively, continuously introducing air for 5min, and removing air in a pipeline;
(2) H is introduced into the air inlet pipe 7 at the rate of 300sccm 2 Introducing CO into the gas inlet 2 at a rate of 100sccm 2 Electrifying the air inlet pipe 7, wherein the power supply frequency is 8kHz, the voltage is 7kv, and the discharge power is 22W; h discharged from the first exhaust hole 8 2 With CO 2 Carrying out pre-reaction in the first discharge area 4 to obtain pre-reaction produced gas, wherein the pre-reaction produced gas comprises CO and methanol;
(3) Gas production by pre-reaction and unreacted CO 2 Entering a second discharge area 5, and introducing normal temperature water, CO and CO into the glass tube heat exchanger at a rate of 100mL/min 2 H discharged from the second exhaust hole 9 2 Reforming reaction is carried out to obtain methanol.
After the reaction is finished, the content of the methanol in the final produced gas is measured by a gas chromatography-mass spectrometer (GC-MS), and the conversion rate of the carbon dioxide is finally measured to be 38.65 percent, and the selectivity of the methanol is 71.3 percent.
Example 2
Methanol was produced from carbon dioxide and hydrogen using the reaction apparatus shown in fig. 1 by the following method:
(1) Introducing carbon dioxide and hydrogen into the insulating tube 1 from an air inlet 2 and an air inlet pipe 7 respectively, continuously introducing air for 5min, and removing air in a pipeline;
(2) H is fed into the gas inlet pipe 7 at a rate of 150sccm 2 Introducing CO into the gas inlet 2 at a rate of 450sccm 2 Electrifying the air inlet pipe 7, wherein the power frequency is 10kHz, the voltage is 8kv, and the discharge power is 28W; h discharged from the first exhaust hole 8 2 With CO 2 Carrying out pre-reaction in the first discharge area 4 to obtain pre-reaction produced gas, wherein the pre-reaction produced gas comprises CO and methanol;
(3) Gas production by pre-reaction and unreacted CO 2 Entering a second discharge area 5, introducing normal temperature water, CO and CO into the glass tube heat exchanger at the speed of 80mL/min 2 H discharged from the second exhaust hole 9 2 Reforming reaction is carried out to obtain methanol.
After the reaction is finished, the content of methanol in the final produced gas is measured by a gas chromatography-mass spectrometer (GC-MS), and the conversion rate of carbon dioxide is finally measured to be 41.4%, and the selectivity of methanol is finally measured to be 76.4%.
Example 3
Methanol was produced using carbon dioxide and hydrogen using the reaction apparatus shown in fig. 1, as follows:
(1) Introducing carbon dioxide and hydrogen into the insulating pipe 1 from an air inlet 2 and an air inlet pipe 7 respectively, continuously introducing air for 5min, and removing air in a pipeline;
(2) H is fed into the gas inlet pipe 7 at a rate of 150sccm 2 Introducing CO into the gas inlet 2 at a rate of 600sccm 2 Electrifying the air inlet pipe 7, wherein the power frequency is 10kHz, the voltage is 8kv, and the discharge power is 30W; h discharged from the first exhaust hole 8 2 With CO 2 Carrying out pre-reaction in the first discharge area 4 to obtain pre-reaction produced gas, wherein the pre-reaction produced gas comprises CO and methanol;
(3) Gas produced by pre-reaction and unreacted CO 2 Entering a second discharge area 5, and introducing normal temperature water, CO and CO into the glass tube heat exchanger at a rate of 90mL/min 2 H discharged from the second exhaust hole 9 2 Reforming reaction is carried out to obtain methanol.
After the reaction is finished, the content of methanol in the final produced gas is measured by a gas chromatography-mass spectrometer (GC-MS), and the conversion rate of carbon dioxide is finally measured to be 51.3%, and the selectivity of methanol is finally measured to be 77.6%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various 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 (10)
1. A reaction device for generating methanol by using carbon dioxide and hydrogen comprises an insulating tube (1), wherein the top of the insulating tube (1) is provided with an air inlet (2), and the bottom of the insulating tube is provided with an air outlet (3); the insulation tube (1) is divided into a first discharge area (4) and a second discharge area (5) from top to bottom, and the volume ratio of the first discharge area (4) to the second discharge area (5) is (3); the first discharge area (4) and the second discharge area (5) are separated by a first screen plate (6); a first catalyst is placed on the first screen plate (6);
the air inlet pipe (7) penetrates through the upper wall of the insulating pipe (1) and extends to the bottom of the insulating pipe (1), and the air inlet pipe (7) is coaxial with the insulating pipe (1); the air inlet pipe (7) is provided with a first exhaust hole (8) and a second exhaust hole (9), the first exhaust hole (8) is located in the first discharge area (4), and the second exhaust hole (9) is located in the second discharge area (5); the air inlet pipe (7) is made of metal;
the metal net (10) is positioned on the outer surface of the first discharge area (4) of the insulating tube (1), and the metal net (10) is connected with the grounding device (11);
the cooling device (12) is positioned on the outer surface of the second discharge area (5) of the insulating tube (1);
the second screen plate (13) is positioned at the bottom of the second discharge area (5), and a second catalyst is placed on the second screen plate;
the grounding device (11) is a metal rod, and the metal rod is connected with a grounding wire;
the metal rod is positioned on the surface of the insulating pipe (1) and is fixed between the metal net (10) and the cooling device (12).
2. The reaction device according to claim 1, wherein the opening area of the first exhaust hole (8) is 60-70% of the cross-sectional area of the intake pipe (7); the opening area of the second exhaust hole (9) is 30-40% of the cross section area of the air inlet pipe (7).
3. The reactor according to claim 1, characterized in that the material of the inlet pipe (7) is 304 stainless steel or 316 stainless steel.
4. A reactor device according to claim 1, wherein the area covered by the metal mesh (10) is 30-35% of the external surface area of the insulating tube (1).
5. The reaction device according to claim 1, wherein the temperature reduction device (12) is a glass tube heat exchanger, and the heat exchange medium of the glass tube heat exchanger is water; the glass tube heat exchanger is provided with a water inlet (14) and a water outlet (15); the coverage area of the glass tube heat exchanger is 30-35% of the external surface area of the insulating tube (1).
6. The reaction device of claim 1, wherein the first catalyst is cu @ al 2 O 3 The second catalyst is Cu/Zn @ Al 2 O 3 。
7. The method for producing methanol using carbon dioxide and hydrogen gas based on the reaction apparatus according to any one of claims 1 to 6, comprising the steps of:
(1) Introducing H into the air inlet pipe (7) 2 Introducing CO into the gas inlet (2) 2 H discharged from the first exhaust hole (8) by energizing the intake pipe (7) 2 With CO 2 Carrying out pre-reaction in the first discharge area (4) to obtain pre-reaction produced gas, wherein the pre-reaction produced gas comprises CO and methanol;
(2) The pre-reaction generates gas and unreacted CO 2 Enters a second discharge area (5) and is subjected to CO and CO under the action of a temperature reduction device (12) 2 H discharged from the second exhaust hole (9) 2 Reforming reaction is carried out to obtain methanol.
8. The method of claim 7, wherein H is 2 With CO 2 The flow ratio of (1) is 3-4.
9. The method according to claim 7, wherein the power supply has a frequency of 7 to 12kHz, a voltage of 5 to 10kV, and a discharge power of 12 to 32W when energized.
10. The method according to claim 7, characterized in that the temperature controlled by the cooling device (12) is between 5 and 30 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110290081.3A CN113070012B (en) | 2021-03-16 | 2021-03-16 | Reaction device and method for generating methanol by using carbon dioxide and hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110290081.3A CN113070012B (en) | 2021-03-16 | 2021-03-16 | Reaction device and method for generating methanol by using carbon dioxide and hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113070012A CN113070012A (en) | 2021-07-06 |
| CN113070012B true CN113070012B (en) | 2023-02-10 |
Family
ID=76613486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110290081.3A Active CN113070012B (en) | 2021-03-16 | 2021-03-16 | Reaction device and method for generating methanol by using carbon dioxide and hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113070012B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114733327B (en) * | 2022-04-19 | 2023-06-23 | 南京工业大学 | CO (carbon monoxide) 2 Integrated device for coupling decomposition and hydrogenation reaction |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546479A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Method and device for epoxidation of propylene using plasma of hydrogen and oxygen |
| WO2013060080A1 (en) * | 2011-10-27 | 2013-05-02 | 大连理工大学 | Method for converting methanol |
| CN104761431A (en) * | 2015-04-22 | 2015-07-08 | 黑龙江科技大学 | Method for preparing methanol by converting coal mine gas under synergistic action of plasma and catalyst |
| CN106748647A (en) * | 2016-11-23 | 2017-05-31 | 亚洲硅业（青海）有限公司 | A kind of carbon dioxide low-temperature plasma hydrogenization method methyl alcohol preparation technology |
| CN107011120A (en) * | 2017-05-09 | 2017-08-04 | 西北大学 | A kind of method of recycling treatment carbon dioxide and water high selectivity ethanol |
| CN107486017A (en) * | 2017-08-30 | 2017-12-19 | 大连民族大学 | A kind of plasma enhancing Ag/Al2O3The method of catalyst removal nitrogen oxides |
| CN109529851A (en) * | 2018-12-26 | 2019-03-29 | 大连海事大学 | A kind of Supported Nickel Catalyst and utilize its plasma-catalytic CO2Preparing methanol by hydrogenation method |
| CN111617714A (en) * | 2020-05-27 | 2020-09-04 | 常州大学 | Catalytic reaction device, instrument for catalyst electrification research and using method |
| CN111921374A (en) * | 2020-08-13 | 2020-11-13 | 浙江工业大学 | Method for catalytic degradation of chlorobenzene by using double-section discharge plasma and preparation method of used catalyst |
| WO2021255422A1 (en) * | 2020-06-15 | 2021-12-23 | The University Of Liverpool | Co2 hydrogenation to oxygenates using plasma catalysis |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140284206A1 (en) * | 2011-10-27 | 2014-09-25 | Dalian University Of Technology | Method for converting methanol |
-
2021
- 2021-03-16 CN CN202110290081.3A patent/CN113070012B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546479A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Method and device for epoxidation of propylene using plasma of hydrogen and oxygen |
| WO2013060080A1 (en) * | 2011-10-27 | 2013-05-02 | 大连理工大学 | Method for converting methanol |
| CN104761431A (en) * | 2015-04-22 | 2015-07-08 | 黑龙江科技大学 | Method for preparing methanol by converting coal mine gas under synergistic action of plasma and catalyst |
| CN106748647A (en) * | 2016-11-23 | 2017-05-31 | 亚洲硅业（青海）有限公司 | A kind of carbon dioxide low-temperature plasma hydrogenization method methyl alcohol preparation technology |
| CN107011120A (en) * | 2017-05-09 | 2017-08-04 | 西北大学 | A kind of method of recycling treatment carbon dioxide and water high selectivity ethanol |
| CN107486017A (en) * | 2017-08-30 | 2017-12-19 | 大连民族大学 | A kind of plasma enhancing Ag/Al2O3The method of catalyst removal nitrogen oxides |
| CN109529851A (en) * | 2018-12-26 | 2019-03-29 | 大连海事大学 | A kind of Supported Nickel Catalyst and utilize its plasma-catalytic CO2Preparing methanol by hydrogenation method |
| CN111617714A (en) * | 2020-05-27 | 2020-09-04 | 常州大学 | Catalytic reaction device, instrument for catalyst electrification research and using method |
| WO2021255422A1 (en) * | 2020-06-15 | 2021-12-23 | The University Of Liverpool | Co2 hydrogenation to oxygenates using plasma catalysis |
| CN111921374A (en) * | 2020-08-13 | 2020-11-13 | 浙江工业大学 | Method for catalytic degradation of chlorobenzene by using double-section discharge plasma and preparation method of used catalyst |
Non-Patent Citations (3)
| Title |
|---|
| Atmospheric Pressure and Room Temperature Synthesis of Methanol through Plasma-Catalytic Hydrogenation of CO2;Li Wang等;《ACS Catalysis》;20170831;第9-19页 * |
| 李尚昆等.CH4/O2等离子体反应直接合成甲醇的研究.《现代化工》.2020,(第010期), * |
| 陈冬等.介质阻挡放电等离子体协同TiO2催化分解CO2的研究.《石河子大学学报(自然科学版)》.2016,(第004期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113070012A (en) | 2021-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rouwenhorst et al. | Plasma-driven catalysis: green ammonia synthesis with intermittent electricity | |
| CN100532249C (en) | Plasma catalyzing process of preparing hydrogen by ammonia decomposition | |
| Zhou et al. | Oxygen-vacancy-mediated catalytic methanation of lignocellulose at temperatures below 200° C | |
| CN101863455B (en) | Plate type plasma reactor for hydrogen production through ammonia decomposition | |
| CN113070012B (en) | Reaction device and method for generating methanol by using carbon dioxide and hydrogen | |
| CN109529851A (en) | A kind of Supported Nickel Catalyst and utilize its plasma-catalytic CO2Preparing methanol by hydrogenation method | |
| AU2007351434A2 (en) | Methods and systems of producing molecular hydrogen using a plasma system | |
| CN110394127B (en) | Fluidized bed methane dry reforming reaction device and method with plasma in-situ coupled ultraviolet light | |
| US7622088B2 (en) | Rapid activation catalyst system in a non-thermal plasma catalytic reactor | |
| Lin et al. | Autothermal reforming of ethanol in a Pd–Ag/Ni composite membrane reactor | |
| CN103601150B (en) | Tube-tube type plasma reactor for preparing hydrogen through ammonia decomposition | |
| Li et al. | The function of porous working electrodes for hydrogen production from water splitting in non-thermal plasma reactor | |
| CN102361816B (en) | Process for producing hydrogen from methanol | |
| CN107011120B (en) | Method for high-selectivity synthesis of ethanol by resource treatment of carbon dioxide and water | |
| JP2005022939A (en) | Reaction device of hydrogen-supply system, and hydrogen-supply system | |
| CN114294130B (en) | Plasma-based ammonia catalytic hydrogen production-ignition integrated system and method | |
| Zhang et al. | Research progress and the prospect of CO2 hydrogenation with dielectric barrier discharge plasma technology | |
| CN112960646B (en) | Reactor for preparing synthesis gas by reforming liquid fuel with plasma and application | |
| Toko et al. | Low-Pressure Methanation of CO2 Using a Plasma–Catalyst System | |
| CN114853566B (en) | Method for preparing ethanol by catalyzing carbon dioxide hydrogenation with plasma | |
| KR20150065386A (en) | Catalyst/plasma fuel reformer for production of hydrogen and vehicle engine system using wasted heat of exhaust gas for vehicle | |
| CN116812867A (en) | On-site hydrogen production device for plasma catalytic reforming methanol and hydrogen production method thereof | |
| JP2005146311A (en) | Fuel reforming device, and method of producing reformed gas | |
| CN114733327B (en) | CO (carbon monoxide) 2 Integrated device for coupling decomposition and hydrogenation reaction | |
| JP4204786B2 (en) | Catalytic reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |