CN108373156A - A method of by carbon dioxide conversion be chemical energy source substance - Google Patents
A method of by carbon dioxide conversion be chemical energy source substance Download PDFInfo
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- CN108373156A CN108373156A CN201810119577.2A CN201810119577A CN108373156A CN 108373156 A CN108373156 A CN 108373156A CN 201810119577 A CN201810119577 A CN 201810119577A CN 108373156 A CN108373156 A CN 108373156A
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Abstract
The invention discloses a kind of by CO2The method for being converted into chemical energy source substance, it includes the following steps：(1) under electric field action, CO2The breakdown electric discharge of gas forms the high temperature CO that temperature is 2000~5000K2Plasma jet；The CO2Plasma includes uncracked CO2And CO2Crack CO, O, the O generated2；(2) CO obtained by step (1)2Plasma jet is in fixed bed reactors further by CO2It is converted into CO；The fixed bed reactors are filled with carbonaceous material or alumina particle.Very dexterously, the present invention utilizes high temperature CO2The hot environment of plasma jet so that while oxygen element in the quick phagic lysis gas of carbonaceous material, utilize carbonaceous material and uncracked CO2Reaction is converted into CO, takes full advantage of CO2The thermal energy that plasma jet carries, rapidly reduces temperature, from reducing temperature and reducing the generation that oxygen element this two reverse side effectively prevents back reaction, realizes stable CO productions, greatly improves CO2Conversion ratio and electric energy service efficiency.
Description
Technical field
The present invention relates to a kind of by CO2The method for being converted into chemical energy source substance.
Background technology
With the lasting use of fossil energy (oil, natural gas and coal), two serious problems are inevitably brought.One
It is since the non-renewable of fossil fuel causes its reserves to gradually decrease and generate energy crisis, second is that fossil fuel
A large amount of uses cause atmospheric carbon dioxide levels increasingly to increase and cause greenhouse effects.Therefore, sustainable energy, such as the sun
Energy, nuclear energy, water energy, wind energy etc. will be as following main energy sources.But such energy is physical energy, usually with electric energy
Form obtains, and not only has time and space limitation in supply, nor can meet human society to hydrocarbon chemical industry original
The demand of material.
In order to solve these problems, using electric energy as cost, the H that will be widely present2O and CO2It is converted into H2And CO, then through industry
It is considered as the unique technical solved these problems that mature F-T synthetic technologys, which prepare chemical energy source substance (carbon hydrocarbon chemicals),
Route becomes each developed country's focus of attention.The essence of the technology path is energy conversion, i.e., converts physical energy (electric energy)
For chemical energy (carbon hydrocarbon materials), result at least generates two great influences to human progress and social sustainable development, i.e.,
Energy resource structure needed for reasonable disposition future society, while reducing GHG carbon dioxide discharge.
Currently, the difficult point of the technology be how low energy consumption, expeditiously by CO2It is converted into CO.The technology hand of generally use
The CO that it catalytic reforming methane technology that section, which has steam reformation coal technology, water vapour, is being developed2Catalytic reforming methane technology and low
Warm non-equilibrium plasma cracks CO2Technology.Steam reformation coal technology is to make water vapour react with red-hot carbon to generate CO
And H2, water vapour catalytic reforming methane technology is to make water vapour react under high temperature catalyst effect with methane to generate CO and H2.Two
Although having industrialized, the heat drive chemical reaction both generated by burning carbonaceous substance not only generates big technology
The CO of amount2Discharge increases carrying capacity of environment, and cannot achieve CO2Emission reduction, to convert Reproduceable electricity to chemical energy final
Purpose.In developing CO2Although catalytic reforming methane technology also converts CO2, but the process overcomes catalyst due to being difficult to
Carbon inactivation is tied on surface, is produced no breakthroughs for a long time.CO is cracked in developing non-equilibrium plasmas2Technology, example
Arc plasma and medium barrier plasma technology are such as slid, high energy electron collision CO is fully relied on2It is allowed to crack, crack
Gas is difficult to that subsequent reactions occur with carbonaceous material, and that there are reaction conversion ratios is low, power consumption is big, and production capacity, which is difficult to amplify, etc. asks
Topic.Therefore, there is an urgent need for a kind of low energy consumption, expeditiously by CO2The method for being converted into CO.
Invention content
In order to electric energy efficiently, low energy consumption by CO2It is converted into CO, the present invention makes CO using electric energy2Gas is breakdown to be put
Electric forming temperature is the high temperature CO of 2000~5000K2Plasma jet.And then, the present invention is directly by high temperature CO2Plasma
Body jet action utilizes this hot environment in carbonaceous material so that uncracked CO2While being converted into CO, utilization is carbon containing
Oxygen element in the quick phagic lysis gas of substance, takes full advantage of CO2The thermal energy that plasma jet carries, rapidly reduces temperature
Degree effectively prevents the generation of back reaction, realizes CO2Low energy consumption, high efficiency are converted into the purpose of CO.
The present invention provides a kind of by CO2The method for being converted into CO, it includes the following steps：
(1) under electric field action, CO2The breakdown electric discharge of gas forms the high temperature CO that temperature is 2000~5000K2Plasma
Body jet stream；The CO2Plasma includes uncracked CO2And CO2Crack CO, O, the O generated2；
(2) CO obtained by step (1)2Plasma jet is in fixed bed reactors further by CO2It is converted into CO；It is described
Fixed bed reactors are filled with carbonaceous material or alumina particle.
It is well known that CO2It is one of most stable of chemical molecular, it is difficult to be cracked into CO and O.The present invention uses gas discharge
Method (such as electric arc) creates hot environment, solves CO2It is difficult to the key problem in technology cracked.Specifically, the present invention uses direct current
Arc-plasma, alternating current arc plasma, rf induction plasma or microwave plasma body technique are sent out in plasma
By CO in raw device2The temperature of gas is increased to 2000K or more so that part CO2Moment it will be cracked into CO and O.
In order to obtain stable CO products, CO back reactions is avoided to generate CO2, the present invention swallows rapidly height using carbonaceous material
Anneal crack vent one's spleen middle oxygen element while be quickly cooled down Pintsch process gas, it is inverse to solve generated CO and O generation using carbonaceous material
Reacting recovery is CO2The problem of.
CO2It is partly cracked into CO, O and O in high-temperature plasma generator2, but under hot environment, pyrolysis product exists
CO again can be with O and O when flowing out plasma discharge region2Reaction reverts to CO again2, eventually lead to extremely low conversion ratio and high
Power consumption, in order to avoid this kind of situation, the present invention utilize the quick phagic lysis gas of carbonaceous material in oxygen element
(chemical principle：C+O=CO, 2C+O2=2CO), effectively prevent the generation of back reaction.Meanwhile the present invention passes through C+CO2
The strong endothermic reaction of=2CO rapidly reduces reaction gas temperature, the CO products stablized.This method both ultrafast cooling plasma
Pyrolysis product, while further obtaining more CO products.
Fixed bed reactors refer to loads particulate solid catalyst or solid reactant in reactor, forms certain altitude
Accumulation bed, while gas or liquid material flow through static fixed bed by particulate interspaces, realize heterogeneous reaction mistake
Journey.The characteristics of this kind of reactor is that the solid particle that is filled in equipment is fixed, is different from solid material and is sent out in equipment
The moving bed and fluid bed of raw movement, also known as packed bed reactor.
In step (1), the electric discharge is direct-current discharge, alternating current discharge, high-frequency discharge or microwave discharge.
In step (1), the CO2The temperature of plasma jet is 3000~3500K.
In step (1), the CO2The flow of gas be 20~100000L/min, preferably 25~1000L/min, it is more excellent
It is selected as 25~500L/min.
In step (1), the CO2It may also include discharge-assisted gas in gas：Ar、N2One or both of；It is described to put
Electricity auxiliary gas and CO2The volume ratio of gas is 1:1~1:1000.
In step (2), the fixed bed reactors are next to plasma jet outlet.
In step (2), the carbonaceous material is in coal, heavy oil, petroleum coke, half coke, coke, stalk, debirs
One or two.
In step (2), the CO2Reaction auxiliary gas can be also passed through in plasma jet：CO2、H2、CH4, coal bed gas,
One or both of biogas.
In order to obtain stable CO products, the present invention is quickly created hot environment by following scheme, swallows high temperature rapidly
Pintsch process gas is quickly cooled down in cracking gas while oxygen element：
The present invention uses H2/C/CH4For chemical coolant, solves generated CO and O generations back reaction and revert to CO2's
Problem.CO2It is partly cracked into CO, O and O in high-temperature plasma generator2, but pyrolysis product is put in outflow plasma
CO again can be with O and O when electric area2Reaction reverts to CO again2, eventually lead to extremely low conversion ratio and high power consumption.This hair
It is bright that following chemical principles, the oxygen element in quick phagic lysis gas is utilized effectively to avoid back reaction.
H2+ O=H2O, 2H2+O2=2H2O,
Or CH4+ O=CO+2H2, CH4+O2=CO+H2+H2O。
Meanwhile the present invention rapidly reduces reaction gas temperature by following strong endothermic reactions, the CO products stablized.
This method both ultrafast cooling plasma cracking product, while further obtaining more CO products.
H2+CO2=H2O+CO,
Or, CH4+CO2=2CO+2H2。
Or, CxHy+zCO2=(x+z) CO+ (z-x) H2O+(0.5y+x-z)H2
The CO2Gas is 1 with the volume ratio for reacting auxiliary gas:2~2:1.
The reaction auxiliary gas can also carry carbon dust.
The carbon dust is 1 with the mass volume ratio for reacting auxiliary gas:10~1:2g/L.
The present invention utilizes electrical energy drive CO2The breakdown electric discharge of gas forms the high temperature CO that temperature is 2000~5000K2Deng from
Daughter jet stream so that CO2CO, O, O are cracked into plasma reactor2.In order to avoid CO, O, O under hot environment2It is inverse
Reaction generates CO2, the present invention is directly by high temperature CO2Plasma jet acts on carbonaceous material, very dexterously, present invention profit
With this hot environment so that while oxygen element in the quick phagic lysis gas of carbonaceous material, using carbonaceous material with do not split
The CO of solution2Reaction is converted into CO, takes full advantage of CO2The thermal energy that plasma jet carries, rapidly reduces temperature, from reduction
This two reverse side effectively prevents CO+O=CO to temperature with reduction oxygen element2Back reaction generation, realize stable CO productions, pole
The earth improves CO2Conversion ratio and electric energy service efficiency.CO2Conversion ratio can reach 95%, produces the power consumption of CO and can be reduced to
320kJ/mol(CO).Specially：
1, the present invention generates CO with electrical energy drive gas discharge2DC arc plasma or CO2Alternating current arc plasma
Body or CO2Rf induction plasma or CO2Microwave plasma creates hot environment；CO2The hot environment (wait from
Daughter generator) in part ground cleave solution be CO, O, O2。
2, the present invention is in immediately high temperature CO2Plasma jet export, installation place carbonaceous material (such as coal, half coke,
Coke, or mixtures thereof and the carbonaceous materials such as stalk, debirs) fixed bed reactors, high-temperature plasma will be come from
O, O of generator2Phagocytosis generates CO.
3, remaining CO in cracking gas2It reacts with carbonaceous material in fixed bed section, continues to generate CO.
4, in immediately high temperature CO2Plasma jet exports, and hydrogen or methane or biomass are sent into plasma jet
Gas or coal bed gas, or these gases of carbon dust are carried, O and O in phagic lysis gas2, generate CO.
5, remaining CO in cracking gas2Occur instead in fixed bed section and above-mentioned gas or the above-mentioned gas for carrying carbon dust
It answers, continues to generate CO.
Obviously, the above according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The specific implementation mode of form by the following examples remakes further specifically the above of the present invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on the above of the present invention
The technology realized all belongs to the scope of the present invention.
Description of the drawings
Figure one is scheme schematic diagram of the present invention by taking DC arc plasma technology as an example.In Fig. 1,1 is discharge-assisted
Gas (such as Ar, N2Deng), 2 be discharge gas CO2, 3 be reaction auxiliary gas (such as CO2、H2、CH4), 4 be high-temperature plasma
Body generator, 5 be discharge-assisted gas (Ar, N2Deng) entrance, 6 be discharge gas CO2Entrance, 7 be reaction auxiliary gas (H2、
CH4) entrance, 8 be fixed bed reactors, and 9 be plasma electrical source, and 10 be gas analysis sample point.
Specific implementation mode
The raw material that is used in the specific embodiment of the invention, equipment are known product, pass through and buy commercial product and obtain.
Embodiment 1
Coke granule is loaded in fixed bed reactors 8, reaction auxiliary gas 3 is closed, by gas 1 (Ar) with the stream of 25L/min
Speed, 2 (CO of gas2) with the flow velocity of 25L/min 4 are sent into from 5,6 respectively, plasma electrical source 9 is opened, which puts for direct current
Electricity, adjustment output power are 14kW, and the high temperature CO that stable temperature is 3100K is formed in 42Plasma jet simultaneously flows into solid
Fixed bed reactor 8, red-hot jet stream flow through the fixed bed reactors 8 of prior loading carbon, and are reacted with carbon and generate CO from fixed bed stream
Go out, reaction product is monitored in 10 sampling analysis of gas analysis sample point after 6 minutes, it is final to realize that efficient, low energy consumption turns with electric energy
Change CO2For the purpose of CO, CO2Conversion ratio can reach 95%, and the power consumption for producing CO is 320kJ/mol (CO).
Embodiment 2
Coke granule is loaded in fixed bed reactors 8, by 1 (N of gas2) with the flow velocity of 25L/min, 2 (CO of gas2) with
The flow velocity of 25L/min is sent into 4 from 5,6 respectively, opens plasma electrical source 9, which is direct-current discharge, and adjustment output power is
14kW forms the high temperature CO that stable temperature is 3100K in 42Plasma jet simultaneously flows out 4, inflow fixed bed reactors
8, open 3 (H of reaction auxiliary gas2), with the flow velocity of 25L/min by hydrogen be sent into red-hot plasma jet and in fixed bed it is anti-
It answers and completes reaction generation CO in device 8, reaction product is monitored in 10 sampling analysis of gas analysis sample point after 6 minutes, it is final to realize
With electric energy, efficient, low energy consumption converts CO2For the purpose of CO, CO2Conversion ratio can reach 60%, and the power consumption for producing CO is
900kJ/mol(CO)。
Embodiment 3
Coke granule is loaded in fixed bed reactors 8, by 1 (N of gas2) with the flow velocity of 25L/min, 2 (CO of gas2) with
The flow velocity of 25L/min is sent into 4 from 5,6 respectively, opens plasma electrical source 9, which is direct-current discharge, and adjustment output power is
14kW forms the high temperature CO that stable temperature is 3100K in 42Plasma jet simultaneously flows out 4, inflow fixed bed reactors
8, open 3 (CH of reaction auxiliary gas4), methane is sent by red-hot plasma jet with the flow velocity of 25L/min and in fixed bed
Reaction is completed in reactor 8 and generates CO, and reaction product is monitored in 10 sampling analysis of gas analysis sample point after 6 minutes, it is final real
Now with electric energy, efficient, low energy consumption converts CO2For the purpose of CO, CO2Conversion ratio can reach 80%, produces the power consumption of CO and can drop
As low as 400kJ/mol (CO).
Embodiment 4
Alumina particle is loaded in fixed bed reactors 8, by 1 (N of gas2) with the flow velocity of 25L/min, 2 (CO of gas2) with
The flow velocity of 25L/min is sent into 4 from 5,6 respectively, opens plasma electrical source 9, which is direct-current discharge, and adjustment output power is
14kW forms the high temperature CO that stable temperature is 3100K in 42Plasma jet simultaneously flows out 4, inflow fixed bed reactors
8, open 3 (H of reaction auxiliary gas2), with the flow velocity of 25L/min by hydrogen carrying carbon dust be sent into red-hot plasma jet and
Reaction is completed in fixed bed reactors 8 and generates CO, wherein the mass volume ratio of carbon dust and hydrogen is 5：15g/L, after 6 minutes
10 sampling analysis of gas analysis sample point monitors reaction product, final to realize that efficient, low energy consumption converts CO with electric energy2For the mesh of CO
, CO2Conversion ratio can reach 80%, produces the power consumption of CO and can be reduced to 400kJ/mol (CO).
Embodiment 5
Alumina particle is loaded in fixed bed reactors 8, by 1 (N of gas2) with the flow velocity of 25L/min, 2 (CO of gas2) with
The flow velocity of 25L/min is sent into 4 from 5,6 respectively, opens plasma electrical source 9, which is direct-current discharge, and adjustment output power is
14kW forms the high temperature CO that stable temperature is 3100K in 42Plasma jet simultaneously flows out 4, inflow fixed bed reactors
8, open 3 (CH of reaction auxiliary gas4), with the flow velocity methane of 25L/min carry carbon dust be sent into red-hot plasma jet and
Reaction is completed in fixed bed reactors 8 and generates CO, wherein the mass volume ratio of carbon dust and methane is 5：15g/L, after 6 minutes
10 sampling analysis of gas analysis sample point monitors reaction product, final to realize that efficient, low energy consumption converts CO with electric energy2For the mesh of CO
, CO2Conversion ratio can reach 90%, produces the power consumption of CO and can be reduced to 350kJ/mol (CO).
Embodiment 6
Alumina particle is loaded in fixed bed reactors 8, by 1 (N of gas2) with the flow velocity of 25L/min, 2 (CO of gas2) with
The flow velocity of 25L/min is sent into 4 from 5,6 respectively, opens plasma electrical source 9, and it is direct-current discharge to adjust the power supply, and whole output power is
14kW forms the high temperature CO that stable temperature is 3100K in 42Plasma jet simultaneously flows out 4, inflow fixed bed reactors
8, open 3 (CO of reaction auxiliary gas2), with the flow velocity CO of 25L/min2It carries carbon dust and is sent into red-hot plasma jet and solid
Reaction is completed in fixed bed reactor 8 and generates CO, wherein carbon dust and CO2Mass volume ratio be 5：15g/mL, in gas after 6 minutes
10 sampling analysis of body analytical sampling point monitors reaction product, final to realize that efficient, low energy consumption converts CO with electric energy2For the mesh of CO
, CO2Conversion ratio can reach 70%, produces the power consumption of CO and can be reduced to 320kJ/mol (CO).
To sum up, the present invention utilizes electrical energy drive CO2The breakdown electric discharge of gas forms the high temperature CO that temperature is 2000~5000K2
Plasma jet so that CO2CO, O, O are cracked into plasma reactor2.In order to avoid CO, O under hot environment,
O2Back reaction generates CO2, the present invention is directly by high temperature CO2Plasma jet acts on carbonaceous material, very dexterously, this hair
It is bright to utilize this hot environment so that while oxygen element in the quick phagic lysis gas of carbonaceous material, using carbonaceous material with
Uncracked CO2Reaction is converted into CO, takes full advantage of CO2The thermal energy that plasma jet carries, rapidly reduces temperature, from
Reducing temperature, this two reverse side effectively prevents CO+O=CO with reduction oxygen element2Back reaction generation, realize stable CO lifes
Production, greatly improves CO2Conversion ratio and electric energy service efficiency.CO2Conversion ratio can reach 95%, and the power consumption for producing CO can
It is reduced to 320kJ/mol (CO).
Claims (10)
1. a kind of by CO2The method for being converted into CO, it is characterised in that：It includes the following steps：
(1) under electric field action, CO2The breakdown electric discharge of gas forms the high temperature CO that temperature is 2000~5000K2Plasma is penetrated
Stream；The CO2Plasma includes uncracked CO2And CO2Crack CO, O, the O generated2；
(2) CO obtained by step (1)2Plasma jet is in fixed bed reactors further by CO2It is converted into CO；The fixation
Bed reactor is filled with carbonaceous material or alumina particle.
2. according to the method described in claim 1, it is characterized in that：In step (1), the electric discharge is direct-current discharge, exchanges and put
Electricity, high-frequency discharge or microwave discharge.
3. according to the method described in claim 1, it is characterized in that：In step (1), the CO2The temperature of plasma jet is
3000~3500K.
4. according to the method described in claim 1, it is characterized in that：In step (1), the CO2The flow of gas be 20~
100000L/min, preferably 25~1000L/min, more preferably 25~500L/min.
5. according to the method described in claim 1, it is characterized in that：In step (1), the CO2It is auxiliary to may also include electric discharge in gas
Help gas：Ar、N2One or both of；The discharge-assisted gas and CO2The volume ratio of gas is 1:1~1:1000.
6. according to the method described in claim 1, it is characterized in that：In step (2), the fixed bed reactors are next to etc. from
Daughter jet exit.
7. according to the method described in claim 1, it is characterized in that：In step (2), the carbonaceous material is coal, heavy oil, stone
One or both of oil coke, half coke, coke, stalk, debirs.
8. according to the method described in claim 1, it is characterized in that：In step (2), the CO2Can also it lead in plasma jet
Enter reaction auxiliary gas：CO2、H2、CH4, coal bed gas, one or both of biogas；The CO2Gas with react auxiliary
The volume ratio of gas is 1:2~2:1.
9. according to the method described in claim 8, it is characterized in that：The reaction auxiliary gas can also carry carbon dust.
10. according to the method described in claim 9, it is characterized in that：The carbon dust and the mass volume ratio for reacting auxiliary gas
It is 1:10~1:2g/L.
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| CN201810119577.2A CN108373156B (en) | 2018-02-06 | 2018-02-06 | Method for converting carbon dioxide into chemical energy substance |
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| CN108373156B CN108373156B (en) | 2019-12-13 |
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Cited By (1)
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| CN115285992A (en) * | 2022-08-25 | 2022-11-04 | 西安电子科技大学 | Plasma-electrolytic coupling decomposition CO for directional separation of products 2 System and method |
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Address after: 610000 Sichuan Jinniu District Chengdu 36 West 1 Street 2 units 18 level 1803 Patentee after: SICHUAN YIJIE TECHNOLOGY Co.,Ltd. Address before: 610000, No. 24, south section of Ring Road, Sichuan, Chengdu Patentee before: SICHUAN University |
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