CN117797634A - Carbon dioxide methanation reaction device and method - Google Patents
Carbon dioxide methanation reaction device and method Download PDFInfo
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- CN117797634A CN117797634A CN202311589995.5A CN202311589995A CN117797634A CN 117797634 A CN117797634 A CN 117797634A CN 202311589995 A CN202311589995 A CN 202311589995A CN 117797634 A CN117797634 A CN 117797634A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 320
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 162
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 160
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 160
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000001257 hydrogen Substances 0.000 claims abstract description 138
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 138
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 137
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 68
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000005192 partition Methods 0.000 claims description 110
- 239000003054 catalyst Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 238000005868 electrolysis reaction Methods 0.000 claims description 41
- 238000006722 reduction reaction Methods 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 230000009849 deactivation Effects 0.000 abstract description 9
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 71
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 28
- 230000001105 regulatory effect Effects 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 11
- 238000009832 plasma treatment Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000010606 normalization Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZMSRCMWBEGLBAI-UHFFFAOYSA-N 3,3,4,4-tetrafluorooxathietane 2,2-dioxide Chemical compound FC1(F)OS(=O)(=O)C1(F)F ZMSRCMWBEGLBAI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention relates to the technical field of carbon dioxide conversion, and discloses a carbon dioxide methanation reaction device and a method. The device comprises a reactor shell (1), wherein a carbon dioxide feed inlet (2) is arranged in the middle of the reactor shell (1), a first product outlet (3) and a second product outlet (4) are respectively arranged at two ends of the reactor shell, a first reaction zone (5) is formed between the carbon dioxide feed inlet (2) and the first product outlet (3), and a second reaction zone (6) is formed between the carbon dioxide feed inlet (2) and the second product outlet (4). According to the carbon dioxide methanation reaction device and method, the catalytic efficiency and the hydrogen utilization rate can be effectively improved, the deactivation rate of a reaction catalyst and the catalytic reaction temperature are reduced, and the aims of energy conservation and emission reduction are fulfilled.
Description
Technical Field
The invention relates to the field of carbon dioxide conversion, in particular to a carbon dioxide methanation reaction device and method.
Background
In recent years, the use of fossil fuels in large quantities has resulted in the emission of large amounts of carbon dioxide in the air, and carbon dioxide is currently the main greenhouse gas responsible for global warming, so that the global environmental problem caused by this has been widely paid attention to various countries. Thus, to realize the CO of the coal-fired power plant 2 Large-scale emission reduction is urgent to solve the problem of CO 2 High added value utilization.
The electric conversion gas (P2G) technique refers to the electrolysis of water into H by using electric energy 2 Post CO 2 Catalytic reaction to CH 4 The method provides a new way for renewable energy sources as a novel energy source conversion and storage mode. The method is divided into 2 stages, redundant electric power in the electric field valley is electrolyzed to produce hydrogen in the first stage, the stage is simple and easy to operate, the energy conversion efficiency can reach 75% -85%, and the existing alkaline water electrolysis hydrogen production technology is very mature and has been applied on a large scale. The second stage is methanation, which is H generated by electrolysis of water under the action of a catalyst 2 And CO 2 The reaction produces methane and water. The energy conversion efficiency of the process is about 75-80%. The electric conversion technology provides a new way for renewable energy sources as a novel energy source conversion and storage mode.
At present, the carbon dioxide methanation technology is considered as one of the most effective technologies for recycling carbon dioxide, so that the reaction for preparing methane by reforming carbon dioxide is attracting more and more attention, on one hand, the reaction effectively and reasonably reduces the emission of carbon dioxide, and on the other hand, the reaction product is methane as combustible matter, and energy is provided. Conventional reactions of carbon dioxide and hydrogen for generating methane generally need to be combined with nickel-based catalysts and the like in a catalytic mode and are carried out under the condition of high temperature and high pressure, however, the catalyst is very easy to deactivate, and the reaction efficiency is greatly reduced.
Therefore, development of a device and a method for methanation of carbon dioxide, which utilize an electroconversion technology to methanation carbon dioxide, realize conversion from inorganic carbon to organic carbon, and solve the problems of low conversion efficiency, high reaction temperature and high deactivation rate of a catalyst, are needed.
Disclosure of Invention
The invention aims to solve the problems of low catalyst conversion efficiency, high reaction temperature, high deactivation rate, low carbon dioxide adsorption amount and the like in the conventional carbon dioxide methanation reaction device and method. The invention provides the carbon dioxide methanation reaction device which applies the hydrogen generated by the electrolyzed water to the carbon dioxide methanation and the reduction of the catalyst, reduces the deactivation rate of the catalyst, saves the time for treating the catalyst, reduces the storage and transportation cost of the hydrogen, and further improves the CO 2 Is a conversion rate of (a). At the same time, provides a method for methanation of carbon dioxide based on the device, provides a method for introducing nitrogen plasma treatment to ensure that the catalyst shows higher reaction activity, reduces the reaction temperature, obviously improves the dispersity of active components and ensures that the catalyst has higher activity on CO 2 The adsorption amount of (2) is also increased.
In order to achieve the above object, according to one aspect of the present invention, there is provided a carbon dioxide methanation reaction device, comprising a reactor housing, wherein a carbon dioxide feed port is provided in the middle of the reactor housing, a first product outlet and a second product outlet are provided at both ends of the reactor housing, a first reaction zone is formed between the carbon dioxide feed port and the first product outlet, and a second reaction zone is formed between the carbon dioxide feed port and the second product outlet.
In the first reaction zone, a first movable partition plate and a first catalytic reaction bed are sequentially arranged in the direction from the carbon dioxide feed inlet to the first product outlet, and a first hydrogen feed inlet is correspondingly arranged in the first reaction zone. In the second reaction zone, a second movable partition plate and a second catalytic reaction bed are sequentially arranged in the direction from the carbon dioxide feed inlet to the second product outlet, and a second hydrogen feed inlet is correspondingly arranged in the second reaction zone.
The first movable partition plate and the second movable partition plate are respectively provided with a check valve, when the first movable partition plate is closed and the second movable partition plate is opened, the first movable partition plate can prevent gas in the second reaction zone from entering the first reaction zone, and redundant hydrogen in the first reaction zone can enter the second reaction zone through the check valves on the first movable partition plate; when the second movable partition is closed and the first movable partition is opened, the second movable partition can prevent gas in the first reaction zone from entering the second reaction zone, and redundant hydrogen in the second reaction zone can enter the first reaction zone through a one-way valve on the second movable partition.
Preferably, the reactor housing is arranged axisymmetrically along the centre line of the carbon dioxide feed inlet.
Preferably, the first product outlet and the second product outlet are respectively provided with a detection device for detecting the concentration of hydrogen and carbon dioxide.
Preferably, the first movable partition and the second movable partition are alternately and cyclically opened.
In a second aspect, the present invention provides a carbon dioxide methanation reaction process carried out in an apparatus as described above, the process comprising the steps of:
(1) Opening a first movable partition plate, closing a second movable partition plate, introducing carbon dioxide from a carbon dioxide feed port, introducing hydrogen generated by electrolysis water from a first hydrogen feed port, and performing carbon dioxide methanation reaction in a first catalytic reaction bed; introducing hydrogen generated by electrolyzed water from a second hydrogen feed inlet, performing catalyst reduction reaction in a second catalytic reaction bed, and discharging a product through a first product outlet;
(2) Opening a second movable partition board, closing the first movable partition board, introducing carbon dioxide from a carbon dioxide feed port, introducing hydrogen generated by electrolysis water from a second hydrogen feed port, and performing carbon dioxide methanation reaction in a second catalytic reaction bed; introducing hydrogen generated by electrolyzed water from a first hydrogen feed inlet, performing catalyst reduction reaction in a first catalytic reaction bed, and discharging a product through a second product outlet;
(3) And (5) alternately performing the step (1) and the step (2).
Preferably, the catalyst comprises a carrier and nickel particles dispersed on the carrier, and the catalyst is subjected to plasma treatment.
Preferably, the carrier is Al 2 O 3 And CeO 2 At least one of (a) and (b).
Preferably, the content of the nickel particles may be 5 to 15 parts by weight, preferably 9 to 11 parts by weight, with respect to 100 parts by weight of the carrier.
Preferably, the carbon dioxide methanation reaction is carried out by the one-way valve through the redundant hydrogen in the catalytic reaction bed of the catalyst reduction reaction.
Preferably, the method further comprises detecting the hydrogen and carbon dioxide concentrations by the detection means for detecting the hydrogen and carbon dioxide concentrations, respectively.
According to the carbon dioxide methanation reaction device, hydrogen generated by electrolysis of water in the electric gas conversion process is simultaneously applied to the carbon dioxide methanation reaction and the reduction reaction of the catalyst, so that the time for treating the catalyst is saved, and the storage and transportation cost of the hydrogen is reduced. And the methanation reaction of carbon dioxide and the reduction reaction of the catalyst are carried out in a partitioned manner, so that the catalyst can be fully reduced, the deactivation rate of the catalyst is reduced, and the conversion rate of carbon dioxide is improved. The redundant hydrogen after being reduced by the catalyst can continuously participate in the methanation reaction of carbon dioxide through the one-way valve, so that the waste or accumulation of the hydrogen is avoided, the full utilization of the hydrogen is realized, and the safety of the device is ensured. By adopting the synthesis method of the device, the catalyst treated by the plasma technology ensures that nickel particles are highly dispersed on the carrier, and the dispersity of active components is obviously improved, thereby improving the catalytic activity and reducing the reaction temperature. Therefore, the carbon dioxide methanation reaction device and the method effectively improve the conversion efficiency of the catalyst, realize the mutual conversion of electric power and natural gas, reduce the load regulation task of a power plant by utilizing trough electricity and ensure the stability of power generation of a boiler.
Drawings
FIG. 1 is a schematic diagram of a carbon dioxide methanation reaction device according to the invention.
Description of the reference numerals
1. A reactor housing; 2. a carbon dioxide feed inlet; 3. a first product outlet; 4. a second product outlet; 5. a first reaction zone; 51. a first movable partition; 52. a first catalytic reaction bed; 53. a first hydrogen feed port; 6. a second reaction zone; 61. a second movable partition; 62. a second catalytic reaction bed; 63. and a second hydrogen feed port.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The carbon dioxide methanation reaction device is shown in fig. 1, and comprises: a reactor shell 1, a carbon dioxide feed inlet 2 is arranged in the middle of the reactor shell 1, a first product outlet 3 and a second product outlet 4 are respectively arranged at two ends, a first reaction zone 5 is formed between the carbon dioxide feed inlet 2 and the first product outlet 3, and a second reaction zone 6 is formed between the carbon dioxide feed inlet 2 and the second product outlet 4 in the reactor shell 1.
In the first reaction zone 5, a first movable partition plate 51 and a first catalytic reaction bed 52 are sequentially arranged in the direction from the carbon dioxide feed inlet 2 to the first product outlet 3, and the first reaction zone 5 is correspondingly provided with a first hydrogen feed inlet 53.
In the second reaction zone 6, a second movable partition 61 and a second catalytic reaction bed 62 are sequentially disposed in a direction from the carbon dioxide feed inlet 2 to the second product outlet 4, and the second reaction zone 6 is correspondingly provided with a second hydrogen feed inlet 63.
The first movable partition plate 51 and the second movable partition plate 61 are respectively provided with a check valve, when the first movable partition plate 51 is closed and the second movable partition plate 61 is opened, the first movable partition plate 51 can prevent the gas in the second reaction zone 6 from entering the first reaction zone 5, and the redundant hydrogen in the first reaction zone 5 can enter the second reaction zone 6 through the check valves on the first movable partition plate 51; when the second movable partition 61 is closed and the first movable partition 51 is opened, the second movable partition 61 can prevent the gas in the first reaction zone 5 from entering the second reaction zone 6, and the redundant hydrogen in the second reaction zone 6 can enter the first reaction zone 5 through the check valve on the second movable partition 61. According to the device provided by the invention, in the process of the methanation reaction of carbon dioxide, the methanation reaction of carbon dioxide and the reduction reaction of the catalyst are carried out in a partitioned manner, and part of hydrogen generated by electrolysis water is led out for the reduction reaction of the catalyst, so that the conversion rate of carbon dioxide and the selectivity of methane are improved, the deactivation rate of the catalyst is reduced, the full utilization of hydrogen and the safety of the device are realized, and the device is suitable for the emission reduction of carbon dioxide and the utilization of surplus power in a power station.
In the apparatus of the present invention, the reactor housing 1 may be arranged axisymmetrically along the center line of the carbon dioxide feed port 2.
In the device according to the invention, in order to ensure that the gas concentration does not exceed the safety range, the first product outlet 3 and the second product outlet 4 are preferably each provided with detection means for detecting the concentration of hydrogen and carbon dioxide.
In the device of the present invention, the detecting device for detecting the concentrations of hydrogen and carbon dioxide may be a concentration detector for hydrogen and carbon dioxide.
In the apparatus according to the present invention, the first movable partition plate 51 and the second movable partition plate 61 are alternately opened in circulation in order to reduce the deactivation rate of the catalyst.
In some embodiments, the carbon dioxide methanation reaction device comprises a reactor shell 1, wherein the reactor shell 1 is symmetrically arranged along the central axis of a carbon dioxide feed inlet 2. The two ends of the reactor shell 1 are respectively provided with a first product outlet 3 and a second product outlet 4, a first reaction zone 5 is formed between the carbon dioxide feed inlet 2 and the first product outlet 3, and a second reaction zone 6 is formed between the carbon dioxide feed inlet 2 and the second product outlet 4 in the reactor shell 1. In the first reaction zone 5, a first movable partition plate 51 and a first catalytic reaction bed 52 are sequentially arranged in the direction from the carbon dioxide feed inlet 2 to the first product outlet 3, and the first reaction zone 5 is correspondingly provided with a first hydrogen feed inlet 53. In the second reaction zone 6, a second movable partition 61 and a second catalytic reaction bed 62 are sequentially disposed in a direction from the carbon dioxide feed inlet 2 to the second product outlet 4, and the second reaction zone 6 is correspondingly provided with a second hydrogen feed inlet 63. The first movable partition plate 51 and the second movable partition plate 61 are respectively provided with a check valve, when the first movable partition plate 51 is closed and the second movable partition plate 61 is opened, the first movable partition plate 51 can prevent the gas in the second reaction zone 6 from entering the first reaction zone 5, and the redundant hydrogen in the first reaction zone 5 can enter the second reaction zone 6 through the check valves on the first movable partition plate 51; when the second movable partition 61 is closed and the first movable partition 51 is opened, the second movable partition 61 can prevent the gas in the first reaction zone 5 from entering the second reaction zone 6, and the redundant hydrogen in the second reaction zone 6 can enter the first reaction zone 5 through the check valve on the second movable partition 61. The first product outlet 3 and the second product outlet 4 are respectively provided with a detection device for detecting the concentration of hydrogen and carbon dioxide. The first movable partition 51 and the second movable partition 61 are alternately opened in a circulation.
The invention also provides a carbon dioxide methanation reaction method, which is carried out in the device and comprises the following steps:
(1) Opening the first movable partition plate 51, closing the second movable partition plate 61, introducing carbon dioxide from the carbon dioxide feed port 2, introducing hydrogen generated by electrolysis of water from the first hydrogen feed port 53, and performing carbon dioxide methanation reaction in the first catalytic reaction bed 52; hydrogen generated by electrolysis water is introduced from a second hydrogen feed port 63, the hydrogen undergoes a catalytic reduction reaction in a second catalytic reaction bed 62, and the product is discharged through a first product outlet 3;
(2) Opening the second movable partition 61, closing the first movable partition 51, introducing carbon dioxide from the carbon dioxide feed port 2, introducing hydrogen generated by electrolysis of water from the second hydrogen feed port 63, and performing carbon dioxide methanation reaction in the second catalytic reaction bed 62; hydrogen generated by electrolysis water is introduced from a first hydrogen feed inlet 53, the hydrogen undergoes a catalytic reduction reaction in a first catalytic reaction bed 52, and the product is discharged through a second product outlet 4;
(3) And (5) alternately performing the step (1) and the step (2).
According to the method, hydrogen generated by electrolysis of water is simultaneously applied to the methanation reaction of carbon dioxide and the reduction reaction of the catalyst, so that the deactivation rate of the catalyst is reduced, the utilization rate of the hydrogen is improved, the storage and transportation cost of the hydrogen is reduced, the conversion rate of carbon dioxide is improved, redundant trough electricity can be utilized, the aim of saving energy and reducing emission is fulfilled, and the method has important significance for realizing sustainable green development of global economy.
In the method of the present invention, the catalyst may include a support and nickel particles dispersed on the support, and the catalyst is preferably subjected to plasma treatment in order to improve the dispersibility of active components and the selectivity of methane, reduce the reaction temperature and improve the carbon deposit resistance.
In the method of the invention, the carrier is Al 2 O 3 And/or CeO 2 Preferably CeO 2 。
In the method of the present invention, the content of the nickel particles may be 5 to 15 parts by weight, preferably 9 to 11 parts by weight, with respect to 100 parts by weight of the carrier.
In the present invention, the catalyst is commercially available or can be prepared according to a conventional method in the art, and a specific preparation method can be referred to the disclosure of patent application CN111359626 a.
In the method of the invention, the carbon dioxide methanation reaction is carried out by the one-way valve through the redundant hydrogen in the catalytic reaction bed of the catalyst reduction reaction.
In the method of the present invention, the method further comprises detecting the concentrations of hydrogen and carbon dioxide, respectively, by the detecting means for detecting the concentrations of hydrogen and carbon dioxide.
In the method of the invention, the airspeed of the carbon dioxide in the methanation reaction of the carbon dioxide can be 6000 to 10000h -1 Preferably 8000-9000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The space velocity of the hydrogen can be 24000-40000h -1 Preferably 32000-36000h -1 。
In the process of the present invention, the conditions in the methanation of carbon dioxide may include: the temperature is 200-350deg.C, preferably 250-300deg.C; the pressure is 0.01-3MPa, preferably 0.1-2.5MPa. Herein, pressure refers to gauge pressure.
In the process of the invention, the space velocity of the hydrogen during the reduction reaction of the catalyst may be 8000-16000h -1 Preferably 10000-15000h -1 。
In the method of the present invention, the conditions in the catalyst reduction reaction may include: the temperature is 600-900 ℃, preferably 700-900 ℃; the pressure is 0.01-3MPa, preferably 0.1-2.5MPa.
In some embodiments, a carbon dioxide methanation reaction process is performed in the apparatus described above, the process comprising:
the plasma-treated catalyst is added to the first catalytic reaction bed 52 and the second catalytic reaction bed 62. The first movable partition plate 51 is opened, the second movable partition plate 61 is closed, and the space velocity is 6000-10000h from the carbon dioxide feed inlet 2 -1 Introducing carbon dioxide, and controlling the space velocity to 24000-40000h from the first hydrogen feeding hole 53 -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in a first catalytic reaction bed 52 at a temperature of 200-350 ℃ and a pressure of 0.01-3 MPa; from the second hydrogen feed port 63 at a space velocity of 8000-16000h -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 600-900 ℃ and the pressure to 0.01-3MPa in the second catalytic reaction bed 62, performing catalyst reduction reaction, and discharging the product through the first product outlet 3; after a period of time, the second movable partition 61 is opened, the first movable partition 51 is closed, and the space velocity from the carbon dioxide feed inlet 2 is 6000-10000h -1 Introducing carbon dioxide, and controlling the space velocity from the second hydrogen inlet 63 to 24000-40000h -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in a second catalytic reaction bed 62 at a temperature of 200-350 ℃ and a pressure of 0.01-3 MPa; from the first hydrogen inlet 53 at a space velocity of 8000-16000h -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 600-900 ℃ and the pressure to 0.01-3MPa in the first catalytic reaction bed 52, performing catalyst reduction reaction, and discharging the product through the second product outlet 4; the above operations are alternately performed. In the reaction process, redundant hydrogen in a catalytic reaction bed of the catalyst reduction reaction is subjected to the carbon dioxide methanation reaction through the one-way valve; the detection device for detecting the concentration of the hydrogen and the concentration of the carbon dioxide respectively detects the concentration of the hydrogen and the concentration of the carbon dioxide.
In other embodiments, a carbon dioxide methanation reaction process is carried out in the apparatus described above, the process comprising:
the plasma-treated catalyst is added to the first catalytic reaction bed 52 and the second catalytic reaction bed 62. The first movable partition plate 51 is opened, the second movable partition plate 61 is closed, and the space velocity is 8000-9000h from the carbon dioxide feed inlet 2 -1 Introducing carbon dioxide, and controlling the space velocity to be 32000-36000h from the first hydrogen feeding hole 53 -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in the first catalytic reaction bed 52 at the temperature of 250-300 ℃ and the pressure of 0.1-2.5 MPa; from the second hydrogen inlet 63 at a space velocity of 10000-15000h -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 700-900 ℃ and the pressure to 0.1-2.5MPa in the second catalytic reaction bed 62, performing catalyst reduction reaction, and discharging the product through the first product outlet 3; after a period of time, the second movable partition 61 is opened, the first movable partition 51 is closed, and the space velocity from the carbon dioxide feed inlet 2 is 8000-9000h -1 Introducing carbon dioxide, and controlling the space velocity to be 32000-36000h from the second hydrogen feeding port 63 -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in a second catalytic reaction bed 62 at the temperature of 250-300 ℃ and the pressure of 0.1-2.5 MPa; from the first hydrogen inlet 53 at a space velocity of 10000-15000h -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 700-900 ℃ and the pressure to 0.1-2.5MPa in the first catalytic reaction bed 52, performing catalyst reduction reaction, and discharging the product through the second product outlet 4; the above operations are alternately performed. In the reaction process, redundant hydrogen in a catalytic reaction bed of the catalyst reduction reaction is subjected to the carbon dioxide methanation reaction through the one-way valve; the detection device for detecting the concentration of the hydrogen and the concentration of the carbon dioxide respectively detects the concentration of the hydrogen and the concentration of the carbon dioxide.
The apparatus and method for continuously synthesizing tetrafluoroethane-beta-sultone according to the present invention will be further described by way of examples. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiment.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below are commercially available unless otherwise specified.
The process of methanation of carbon dioxide in the following examples is carried out in the apparatus shown in FIG. 1, and specifically, the apparatus includes a reactor housing 1, and the reactor housing 1 is arranged axisymmetrically along the center line of a carbon dioxide feed port 2. The two ends of the reactor shell 1 are respectively provided with a first product outlet 3 and a second product outlet 4, a first reaction zone 5 is formed between the carbon dioxide feed inlet 2 and the first product outlet 3, and a second reaction zone 6 is formed between the carbon dioxide feed inlet 2 and the second product outlet 4 in the reactor shell 1. In the first reaction zone 5, a first movable partition plate 51 and a first catalytic reaction bed 52 are sequentially arranged in the direction from the carbon dioxide feed inlet 2 to the first product outlet 3, and the first reaction zone 5 is correspondingly provided with a first hydrogen feed inlet 53. In the second reaction zone 6, a second movable partition 61 and a second catalytic reaction bed 62 are sequentially disposed in a direction from the carbon dioxide feed inlet 2 to the second product outlet 4, and the second reaction zone 6 is correspondingly provided with a second hydrogen feed inlet 63. The first movable partition plate 51 and the second movable partition plate 61 are respectively provided with a check valve, when the first movable partition plate 51 is closed and the second movable partition plate 61 is opened, the first movable partition plate 51 can prevent the gas in the second reaction zone 6 from entering the first reaction zone 5, and the redundant hydrogen in the first reaction zone 5 can enter the second reaction zone 6 through the check valves on the first movable partition plate 51; when the second movable partition 61 is closed and the first movable partition 51 is opened, the second movable partition 61 can prevent the gas in the first reaction zone 5 from entering the second reaction zone 6, and the redundant hydrogen in the second reaction zone 6 can enter the first reaction zone 5 through the check valve on the second movable partition 61. The first product outlet 3 and the second product outlet 4 are respectively provided with a detection device for detecting the concentration of hydrogen and carbon dioxide. The first movable partition 51 and the second movable partition 61 are alternately opened in a circulation.
Example 1
To the first catalytic reaction bed 52 and the second catalytic reaction bed 62, 50g of the nickel-based catalyst after the plasma treatment (synthesized according to the method of patent application CN111359626 a) was added. The first movable partition plate 51 was opened, the second movable partition plate 61 was closed, and the space velocity from the carbon dioxide feed port 2 was 8000h -1 Introducing carbon dioxide, and controlling the space velocity to be 32000h from the first hydrogen feeding hole 53 -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in the first catalytic reaction bed 52 at the temperature of 270 ℃ and the pressure of 0.1 MPa; at a space velocity of 10000h from the second hydrogen feed port 63 -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 700 ℃ and the pressure to 0.1MPa in the second catalytic reaction bed 62, performing catalyst reduction reaction, and discharging the product through the first product outlet 3; after a while, the second movable partition 61 was opened and the first movable partition 51 was closed, and the space velocity from the carbon dioxide feed port 2 was 8000h -1 Introducing carbon dioxide, and controlling the space velocity to 32000h from the second hydrogen feeding port 63 -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in the second catalytic reaction bed 62 at the temperature of 270 ℃ and the pressure of 0.1 MPa; at a space velocity of 10000h from the first hydrogen feed port 53 -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 700 ℃ and the pressure to 0.1MPa in the first catalytic reaction bed 52, performing catalyst reduction reaction, and discharging the product through the second product outlet 4; the above operations are alternately performed.
Introducing the product gas into gas chromatography with stable operation for sampling analysis; CO 2 Conversion from N 2 -internal standard measurement, methane selectivity is calculated by C-based internal normalization; the calculated data are shown in Table 1.
Example 2
To the first catalytic reaction bed 52 and the second catalytic reaction bed 62, 50g of the nickel-based catalyst after the plasma treatment (synthesized according to the method of patent application CN111359626 a) was added. The first movable partition plate 51 was opened, the second movable partition plate 61 was closed, and the space velocity from the carbon dioxide feed port 2 was 8500h -1 Introducing carbon dioxide, and controlling the space velocity to 34000h from the first hydrogen feeding port 53 -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in the first catalytic reaction bed 52 at the temperature of 250 ℃ and the pressure of 1.5 MPa; at a space velocity of 12000h from the second hydrogen feed port 63 -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 800 ℃ and the pressure to 1.5MPa in the second catalytic reaction bed 62, performing catalyst reduction reaction, and discharging the product through the first product outlet 3; after a while, the second movable partition 61 was opened and the first movable partition 51 was closed, and the space velocity from the carbon dioxide feed port 2 was 8500h -1 Introducing carbon dioxide from the second hydrogen inlet 63 at a space velocity of 34000h -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in a second catalytic reaction bed 62 at the temperature of 250 ℃ and the pressure of 1.5 MPa; at a space velocity of 12000h from the first hydrogen feed inlet 53 -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 800 ℃ and the pressure to 1.5MPa in the first catalytic reaction bed 52, performing catalyst reduction reaction, and discharging the product through the second product outlet 4; the above operations are alternately performed.
Introducing the product gas into gas chromatography with stable operation for sampling analysis; CO 2 Conversion from N 2 -internal standard measurement, methane selectivity is calculated by C-based internal normalization; the calculated data are shown in Table 1.
Example 3
To the first catalytic reaction bed 52 and the second catalytic reaction bed 62, 50g of the nickel-based catalyst after the plasma treatment (synthesized according to the method of patent application CN111359626 a) was added. The first movable partition plate 51 was opened, the second movable partition plate 61 was closed, and the space velocity from the carbon dioxide feed port 2 was 9000h -1 Introducing carbon dioxide, and controlling the space velocity to be 36000h from the first hydrogen feeding hole 53 -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in the first catalytic reaction bed 52 at a temperature of 300 ℃ and a pressure of 2.5 MPa; at a space velocity of 15000h from the second hydrogen feed port 63 -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 900 ℃ and the pressure to 2.5MPa in the second catalytic reaction bed 62, performing catalyst reduction reaction, and discharging the product through the first product outlet 3; after a period of time, openA second movable partition 61 closing the first movable partition 51 and having a space velocity of 9000h from the carbon dioxide feed inlet 2 -1 Introducing carbon dioxide, and controlling the space velocity to be 36000h from the second hydrogen feeding port 63 -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in the second catalytic reaction bed 62 at a temperature of 300 ℃ and a pressure of 2.5 MPa; at a space velocity of 15000h from the first hydrogen feed port 53 -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 900 ℃ and the pressure to 2.5MPa in the first catalytic reaction bed 52, performing catalyst reduction reaction, and discharging the product through the second product outlet 4; the above operations are alternately performed.
Introducing the product gas into gas chromatography with stable operation for sampling analysis; CO 2 Conversion from N 2 -internal standard measurement, methane selectivity is calculated by C-based internal normalization; the calculated data are shown in Table 1.
Comparative example 1
To the first catalytic reaction bed 52 and the second catalytic reaction bed 62, 50g of nickel-based catalyst (synthesized according to the method of patent application CN111359626 a) was added. The first movable partition plate 51 was opened, the second movable partition plate 61 was closed, and the space velocity from the carbon dioxide feed port 2 was 8500h -1 Introducing carbon dioxide, and controlling the space velocity to 34000h from the first hydrogen feeding port 53 -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in the first catalytic reaction bed 52 at the temperature of 400 ℃ and the pressure of 0.2 MPa; at a space velocity of 12000h from the second hydrogen feed port 63 -1 Introducing hydrogen generated by electrolysis water, regulating the temperature to 800 ℃ and the pressure to 0.2MPa in the second catalytic reaction bed 62, performing catalyst reduction reaction, and discharging the product through the first product outlet 3; after a while, the second movable partition 61 was opened and the first movable partition 51 was closed, and the space velocity from the carbon dioxide feed port 2 was 8500h -1 Introducing carbon dioxide from the second hydrogen inlet 63 at a space velocity of 34000h -1 Introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in the second catalytic reaction bed 62 at the temperature of 400 ℃ and the pressure of 0.2 MPa; at a space velocity of 12000h from the first hydrogen feed inlet 53 -1 Introducing hydrogen generated by electrolysis of water, at the first stageIn the catalytic reaction bed 52, the temperature is regulated to 800 ℃ and the pressure is regulated to 0.2MPa, the catalyst reduction reaction is carried out, and the product is discharged through the second product outlet 4; the above operations are alternately performed.
Introducing the product gas into gas chromatography with stable operation for sampling analysis; CO 2 Conversion from N 2 -internal standard measurement, methane selectivity is calculated by C-based internal normalization; the calculated data are shown in Table 1.
Comparative example 2
50g of the nickel-based catalyst after the plasma treatment (synthesized according to the method of patent application CN111359626 a) was added to the first catalytic reaction bed 52. The first movable partition plate 51 was opened, the second movable partition plate 61 was closed, and the space velocity from the carbon dioxide feed port 2 was 8500h -1 Introducing carbon dioxide, and controlling the space velocity to 34000h from the first hydrogen feeding port 53 -1 And introducing hydrogen generated by electrolysis water, and performing carbon dioxide methanation reaction in the first catalytic reaction bed 52 at the temperature of 280 ℃ and the pressure of 0.2 MPa.
Introducing the product gas into gas chromatography with stable operation for sampling analysis; CO 2 Conversion from N 2 -internal standard measurement, methane selectivity is calculated by C-based internal normalization; the calculated data are shown in Table 1.
TABLE 1
| CO 2 Conversion rate | Methane selectivity | |
| Example 1 | 98 | 99.6 |
| Example 2 | 99 | 100 |
| Example 3 | 98 | 99.8 |
| Comparative example 1 | 83 | 91.7 |
| Comparative example 2 | 89 | 96.2 |
As can be seen from the results in Table 1, the examples of the carbon dioxide methanation reaction device and method have higher carbon dioxide conversion rate and methane selectivity, which show that the device and method can effectively improve the catalytic efficiency and reduce the deactivation rate and reaction temperature of the catalyst.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A carbon dioxide methanation reaction device, which is characterized by comprising a reactor shell (1), wherein a carbon dioxide feed inlet (2) is arranged in the middle of the reactor shell (1), a first product outlet (3) and a second product outlet (4) are respectively arranged at two ends of the reactor shell, a first reaction zone (5) is formed between the carbon dioxide feed inlet (2) and the first product outlet (3), and a second reaction zone (6) is formed between the carbon dioxide feed inlet (2) and the second product outlet (4);
a first movable partition plate (51) and a first catalytic reaction bed (52) are sequentially arranged in the first reaction zone (5) in the direction from the carbon dioxide feed inlet (2) to the first product outlet (3), and a first hydrogen feed inlet (53) is correspondingly arranged in the first reaction zone (5);
a second movable partition plate (61) and a second catalytic reaction bed (62) are sequentially arranged in the second reaction zone (6) from the carbon dioxide feed inlet (2) to the second product outlet (4), and a second hydrogen feed inlet (63) is correspondingly arranged in the second reaction zone (6);
the first movable partition plate (51) and the second movable partition plate (61) are respectively provided with a one-way valve, when the first movable partition plate (51) is closed and the second movable partition plate (61) is opened, the first movable partition plate (51) can prevent gas in the second reaction zone (6) from entering the first reaction zone (5), and redundant hydrogen in the first reaction zone (5) can enter the second reaction zone (6) through the one-way valves on the first movable partition plate (51); when the second movable partition plate (61) is closed and the first movable partition plate (51) is opened, the second movable partition plate (61) can prevent gas in the first reaction zone (5) from entering the second reaction zone (6), and redundant hydrogen in the second reaction zone (6) can enter the first reaction zone (5) through a one-way valve on the second movable partition plate (61).
2. The apparatus according to claim 1, characterized in that the reactor housing (1) is arranged axisymmetrically along the centre line of the carbon dioxide feed opening (2).
3. The device according to claim 1 or 2, characterized in that the first product outlet (3) and the second product outlet (4) are each provided with detection means for detecting the concentration of hydrogen and carbon dioxide.
4. The device according to claim 1 or 2, characterized in that the first movable partition (51) and the second movable partition (61) are alternately cyclically opened.
5. A process for methanation of carbon dioxide, characterized in that it is carried out in a plant according to any one of claims 1 to 4, comprising the steps of:
(1) Opening the first movable partition plate (51), closing the second movable partition plate (61), introducing carbon dioxide from the carbon dioxide feed port (2), introducing hydrogen generated by electrolysis water from the first hydrogen feed port (53), and performing carbon dioxide methanation reaction in the first catalytic reaction bed (52); introducing hydrogen generated by electrolysis water from a second hydrogen feed inlet (63), performing catalyst reduction reaction in a second catalytic reaction bed (62), and discharging a product through a first product outlet (3);
(2) Opening a second movable partition plate (61), closing the first movable partition plate (51), introducing carbon dioxide from a carbon dioxide feed port (2), introducing hydrogen generated by electrolysis of water from a second hydrogen feed port (63), and performing carbon dioxide methanation reaction in a second catalytic reaction bed (62); introducing hydrogen generated by electrolysis water from a first hydrogen feed inlet (53), performing catalyst reduction reaction in a first catalytic reaction bed (52), and discharging a product through a second product outlet (4);
(3) And (5) alternately performing the step (1) and the step (2).
6. The method of claim 5, wherein the catalyst comprises a support and nickel particles dispersed on the support, and the catalyst is plasma treated.
7. The method of claim 6, wherein the support is Al 2 O 3 And CeO 2 At least one of (a) and (b).
8. The method according to claim 6 or 7, characterized in that the nickel particles may be contained in an amount of 5-15 parts by weight, preferably 9-11 parts by weight, relative to 100 parts by weight of the carrier.
9. The method according to any one of claims 5-8, characterized in that excess hydrogen in the catalytic bed of the catalyst reduction reaction is passed through the one-way valve for the methanation of carbon dioxide.
10. The method of claim 5, further comprising detecting hydrogen and carbon dioxide concentrations by the means for detecting hydrogen and carbon dioxide concentrations, respectively.
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