CN117839377A - Capturing and converting integrated system based on carbon dioxide adsorption and catalysis dual-function material - Google Patents
Capturing and converting integrated system based on carbon dioxide adsorption and catalysis dual-function material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 85
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 67
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 47
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 32
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 20
- 239000003463 adsorbent Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 230000008929 regeneration Effects 0.000 claims abstract description 12
- 238000011069 regeneration method Methods 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
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- 238000000034 method Methods 0.000 claims description 69
- 230000008569 process Effects 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 30
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 230000001588 bifunctional effect Effects 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000011343 solid material Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
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- 239000000203 mixture Substances 0.000 claims description 11
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- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 28
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Abstract
The invention relates to the technical field of carbon dioxide trapping and utilization, and discloses a trapping and conversion integrated system based on a carbon dioxide adsorption catalysis dual-function material, which comprises a fixed bed reactor A and a fixed bed reactor B, and the fixed bed reactionOne end of the reactor A is connected with one end of the fixed bed reactor B through a first four-way reversing valve, the other end of the fixed bed reactor A is connected with the other end of the fixed bed reactor B through a second four-way reversing valve, adsorption and catalysis difunctional materials are filled on the two fixed bed reactors, the adsorption and catalysis difunctional materials are composed of alkali metal adsorbents and transition metal catalysts, and the two fixed bed reactors are periodically switched by two working modes to realize circulation. The invention utilizes the adsorption and catalysis dual-function material, and can adsorb CO in the air at normal temperature 2 Methane is prepared by directly heating hydrogenation catalytic reaction without desorption after adsorption, and meanwhile, the regeneration of the adsorbent is realized, and the low-energy consumption and integrated CO is realized 2 And (5) capturing and recycling.
Description
Technical Field
The invention relates to the technical field of carbon dioxide trapping and utilization, in particular to a trapping and conversion integrated system based on a carbon dioxide adsorption catalysis dual-function material, which can be used for trapping and recycling carbon dioxide in air.
Background
Carbon capture is largely divided into two paths depending on the source of carbon dioxide: carbon Capture and Sequestration (CCS) and direct air carbon capture (DAC). The former is also called as 'flue gas capture', namely capturing carbon from power plants and industrial waste gas, and the technology maturity is higher at present; the latter, as the name suggests, is a new generation of carbon capture technology where carbon dioxide originates from natural air. The traditional CCUS technology is divided into two sections for CO 2 Trapping and storing or converting and utilizing, in recent years, renewable power hydrogen production technology is rapidly developed, hydrogen production cost is continuously reduced, and if CO is utilized 2 The energy required by the desorption, purification and conversion utilization processes does not change CO 2 The regeneration of the adsorbent and CO are realized simultaneously through hydrogenation catalytic reaction under the desorption condition 2 Realize the utilization of resources of CO 2 Integrated CO capture and utilization 2 capture and utilization, ICCU), will have huge energy saving and consumption reduction advantages.
Very low CO in air 2 The partial pressure (40 Pa) brings about high energy consumption and high cost, and is a main problem for limiting the commercial application of DAC technology. Currently mainstreamDAC technology uses organic amine loaded porous carrier as solid adsorbent, its adsorption capacity is high, but CO 2 The desorption of the adsorbent is the regeneration process of the adsorbent requires higher energy consumption. After which the desorbed CO is required 2 If the sealing is carried out, additional transportation and storage cost, leakage, environmental influence and other potential risks are brought; when the CO is used, the collected CO is used 2 Conversion to renewable fuels or high value chemicals requires separation and purification to obtain high purity CO 2 This process further increases energy consumption and is subject to CO 2 Low conversion, poor selectivity, unconverted CO 2 Escape, etc. Thus, existing DAC technology based on solid amine adsorbents still face significant technical challenges.
Disclosure of Invention
The ICCU technology is mainly applied to the carbon capture of the flue gas at present, namely, the CO in the waste gas of power plants, traffic and industry is carried out based on adsorption catalysis dual-functional materials (DFM) 2 Is captured and catalytically converted into valuable fuels or production materials. Although CO is in the flue gas 2 The concentration (about 15% by volume) is relatively high with respect to air, but the flue gas also contains a certain amount of pollutants (such as NOx, SOx, particulate matter, etc.) which can adversely affect the performance of the adsorbent and catalyst. Furthermore, conventional ICCU techniques are geographically limited and the system needs to be placed near the emission source. DAC-ICCU is based on an adsorption catalysis dual-functional material composed of an alkali metal adsorbent and a transition metal catalyst, and is used for adsorbing CO at normal temperature 2 No CO is absorbed 2 Desorption, directly hydrogenating to prepare methane by utilizing renewable electric power, and realizing the regeneration of the adsorbent. The technology avoids the regeneration of adsorbent and CO with high energy consumption 2 And in the separation, purification and conversion utilization process, the system has compact structure, and can realize distributed carbon emission reduction and high-efficiency energy utilization.
The invention provides a capturing and converting integrated system based on carbon dioxide adsorption catalysis difunctional materials, which comprises a fixed bed reactor A and a fixed bed reactor B, wherein one end of the fixed bed reactor A is connected with one end of the fixed bed reactor B through a first four-way reversing valve, the other end of the fixed bed reactor A is connected with the other end of the fixed bed reactor B through a second four-way reversing valve, adsorption catalysis difunctional materials are filled on the fixed bed reactor A and the fixed bed reactor B, and the adsorption catalysis difunctional materials are formed based on alkali metal adsorbents and transition metal catalysts;
the fixed bed reactor A and the fixed bed reactor B are periodically switched by two working modes to realize circulation, and the first working mode is as follows: the fixed bed reactor A is filled with air to carry out the trapping process, and the fixed bed reactor B with the trapping completed is filled with H 2 Carrying out a conversion process; the second working mode is as follows: after the chemical reactions in the fixed bed reactor A and the fixed bed reactor B reach equilibrium, the air inlet of the fixed bed reactor A and the air inlet of the fixed bed reactor B are switched through the first four-way reversing valve, the temperature of the fixed bed reactor A is changed, the temperature of the fixed bed reactor A is raised to about 300 ℃, and H is introduced 2 Finishing conversion and adsorbent regeneration, cooling the fixed bed reactor B to normal temperature, and introducing air to finish CO 2 And capturing, namely completing replacement from the first working mode to the second working mode.
Further, the H 2 Produced by a hydrogen production machine powered by renewable electricity to produce H 2 The renewable power comprises photoelectrical power and wind power.
Further, the adsorption catalysis dual-function material consists of an adsorbent, a catalyst and a carrier, wherein the adsorbent adopts alkali metal and comprises K 2 CO 3 、Na 2 CO 3 One or more of MgO, the catalyst realizes a hydroconversion process and comprises one or more of Ru, ni, co, pt, and the carrier comprises Al 2 O 3 、SiO 2 、CeO 2 One or more of (a) and (b);
the adsorbent and catalyst are uniformly dispersed on a carrier having a set specific surface area and pore structure to enhance the contact and mass transfer process with the gas stream.
Further, the adsorbent is denoted as M, the catalyst is denoted as A, the carrier is denoted as S, the respective mass percentages of the components M, A, S in the adsorption catalysis dual-function material are x, y and z, wherein x is 0.1-0.4, y is 0.005-0.05, and z is 1-x-y.
Further, the adsorption catalysis dual-function material is prepared by adopting an impregnation method or a one-pot method; for the impregnation method, the adsorbent and the catalyst are loaded on the carrier, and the two components are impregnated simultaneously or sequentially, namely, the adsorbent is impregnated first and then the catalyst is impregnated, or the catalyst is impregnated first and then the adsorbent is impregnated; for the one-pot method, the adsorbent, the catalyst and the carrier metal precursor salt are dissolved in deionized water together, citric acid is added as a complexing agent, the mixture is heated and stirred to form sol, then the sol is dried to obtain puffed solid, and finally the puffed solid is calcined to obtain the bifunctional material with uniformly dispersed elements.
Further, ru-K is used 2 CO 3 -Al 2 O 3 As the adsorption-catalysis dual-function material, wherein K 2 CO 3 Is adsorbent, ru is catalyst, is loaded on Al 2 O 3 A carrier;
Ru-K 2 CO 3 -Al 2 O 3 direct air CO adsorbing catalytic double function material 2 The trapping and conversion integrated mechanism mode is as follows: CO in air at normal temperature 2 And H is 2 O、K 2 CO 3 Generating KHCO by chemical reaction 3 The method specifically comprises the following steps: CO 2 +H 2 O+K 2 CO 3 →2KHCO 3 ，CO 2 Is trapped on the adsorbent site, after the adsorption reaches saturation, the fixed bed reactor A is heated to about 300 ℃, under the action of Ru catalyst, H 2 To H atoms, then transferred from the catalytic site to the vicinity of the adsorption site, and adsorbed CO 2 Generating subsequent reaction to generate CH 4 At the same time regenerating the adsorbent to K 2 CO 3 The method specifically comprises the following steps: 2KHCO 3 +4H 2 →K 2 CO 3 +CH 4 +3H 2 O, the regenerated material can be adsorbed and converted for the next time, so that the recycling is realized.
Further, ru-K 2 CO 3 -Al 2 O 3 The adsorption catalysis bifunctional material is prepared by adopting an impregnation method and comprises the following specific steps:
precursor of metalPreparing solution of the salt according to the proportion: 0.07gK 2 CO 3 With 0.0410g RuCl 3 H 2 O was dispersed in 0.3g deionized water, followed by adding 0.43g Al to the solution 2 O 3 Wherein Al is 2 O 3 The mass of the water is obtained according to the proportion calculation, and the water is mixed and stirred until the water is naturally volatilized; and then drying the solid in a 100 ℃ oven for 24 hours to obtain a dry solid, grinding the dry solid, placing the dry solid in a muffle furnace, heating the dry solid to 300 ℃ at a heating rate of 5 ℃/min, calcining the dry solid for 1 hour, and finally tabletting and granulating the obtained solid material, and sieving the solid material to obtain the solid material with a particle size of 40-60 meshes.
Ru-K 2 CO 3 -Al 2 O 3 The adsorption catalysis bifunctional material is prepared by adopting a one-pot method and comprises the following specific steps:
preparing a solution of metal precursor salt according to the proportion: 0.5g KNO 3 、1.8553gAl(NO 3 ) 3 ·9H 2 O and 0.0205g RuCl 3 H 2 O was dispersed in 7.12ml deionized water, and after stirring well 1.9003g citric acid was added and stirred vigorously at 80℃until a sol-like substance was formed. Drying the sol-like substance in a 120 ℃ oven overnight to obtain a puffed solid, grinding the puffed solid into powder, placing the powder in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min, calcining for 4 hours, and finally tabletting and granulating the obtained solid material, and sieving the solid material to obtain the solid material with a particle size of 40-60 meshes.
Further, ru-K 2 CO 3 -Al 2 O 3 The specific experimental operation flow of the adsorption catalysis bifunctional material applied to a single fixed bed reactor is as follows:
s1, preprocessing, namely reducing RuO into Ru, so that the bifunctional material has catalytic activity: 100mg of material is placed in a fixed bed reactor, the temperature is raised to 350 ℃, 40% H is introduced 2 /N 2 The mixture is purged and activated for 1 hour;
s2, introducing pure N 2 Purging until no H is detected in the effluent stream 2 ；
S3、CO 2 The trapping process comprises the following steps: 400ppm CO is introduced at normal temperature 2 /21％O 2 /N 2 The mixed gas and the set quantity of water vapor are used for simulating trueAir in real environment, K in the process 2 CO 3 CO capture 2 Generating KHCO 3 Stopping ventilation after the material reaches adsorption saturation;
s4, introducing pure N 2 Purging;
s5, a conversion process: heating the fixed bed reactor to 300-350 ℃, and introducing 40% H 2 /N 2 Mixture gas, CO adsorbed under the action of Ru catalyst 2 And H is 2 Obtaining a target product CH by reaction 4 And regenerating the adsorbent to K 2 CO 3 Continuous aeration to CH in reactor effluent stream 4 Concentration is lower than 100ppm;
s6, introducing pure N 2 Purging until no H is detected in the effluent stream 2 ；
And S7, repeating the steps S1-S6 to finish recycling, wherein the steps S1-S6 are all carried out under normal pressure.
The beneficial effects of the invention are as follows:
1. through adsorption and catalysis of the difunctional material, CO in the air is realized simultaneously 2 Is used for capturing and converting CO 2 After trapping, the methane can be directly subjected to hydroconversion and utilization to prepare methane as fuel without release, purification and storage, so that the high-efficiency utilization of energy and the great simplification of a system are realized.
2. By adopting the method of the invention, the high CO can be prepared 2 Adsorption capacity, high methane conversion, high cycle stability, low energy consumption CO 2 The adsorption-catalysis dual-function material has the advantages of simple preparation process (an impregnation method or a one-pot method), short growth period, high productivity and low cost.
3. The dual-functional material and the trapping and conversion integrated system prepared by the material can realize CO in the air 2 Continuously capturing and utilizing renewable power to prepare green hydrogen, directly regenerating adsorbent and preparing methane, solving the problem of CO 2 Capturing and converting CO in two steps 2 High energy consumption and complex system in the processes of release, separation, storage and conversion.
Drawings
FIG. 1 is a schematic view ofDirect air CO in the present invention 2 The structure of the capture conversion integrated (DAC-ICCU) system is schematically shown.
FIG. 2 shows the K of the present invention 2 CO 3 -Ru/Al 2 O 3 The adsorption and hydroconversion integrated mechanism of the bifunctional material is schematically shown.
FIG. 3 shows the K of the present invention 2 CO 3 -Ru/Al 2 O 3 Gas concentration change diagram of dual-functional material adsorption and hydro-conversion stage.
FIG. 4 is a view of the Na of the present invention 2 CO 3 -Ru/Al 2 O 3 Gas concentration change diagram of dual-functional material adsorption and hydro-conversion stage.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a direct air CO based on adsorption catalysis dual-function material 2 Capturing and converting integrated (DAC-ICCU) technology, adsorption and catalysis dual-function material based on alkali metal adsorbent and transition metal catalyst is utilized to adsorb CO at normal temperature 2 Methane is prepared by directly heating and hydrogenating without desorption after adsorption, and the regeneration of adsorbent and CO are realized 2 Is used for recycling. Meanwhile, the defects of the traditional DAC technology and ICCU technology are avoided: adsorbent regeneration and CO without high energy consumption 2 The separation, purification and conversion utilization processes are performed, and the system structure is compact; CO capture from air 2 The DAC has no pollution gas influence, no regional limitation, and greater flexibility, can integrate the DAC device into a renewable energy system, and can realize distributed carbon emission reduction and efficient energy utilization.
Aiming at the coupling problem of DAC and ICCU, the technical proposal of the invention provides a complete set of direct air CO 2 Capturing and converting integrated (DAC-ICCU) system capable of realizing CO in air 2 Is collected and utilized. Filling a fixed bed reactor with an alkali metal-based adsorbent and a peroxideAdsorption catalysis double-function material composed of transition metal catalyst and prepared from alkali metal to CO 2 The adsorption of carbonate or bicarbonate is generated to realize air carbon capture at room temperature; hydrogenation of carbonate or bicarbonate to prepare CH under the action of transition metal catalyst 4 Thereby effecting the conversion process and regeneration of the adsorbent. The continuous process of trapping and catalytic conversion is realized through the design of a double-reactor trapping and conversion integrated system, and the specific structure is shown in figure 1.
As shown in fig. 1, the integrated system for capturing and converting based on carbon dioxide adsorption catalysis difunctional material provided by the invention comprises a fixed bed reactor A and a fixed bed reactor B, wherein one end of the fixed bed reactor A is connected with one end of the fixed bed reactor B through a first four-way reversing valve, the other end of the fixed bed reactor A is connected with the other end of the fixed bed reactor B through a second four-way reversing valve, adsorption catalysis difunctional material is filled on the fixed bed reactor A and the fixed bed reactor B, and the adsorption catalysis difunctional material is composed of an alkali metal adsorbent and a transition metal catalyst;
the fixed bed reactor A and the fixed bed reactor B are periodically switched by two working modes to realize circulation, and the first working mode is as follows: the fixed bed reactor A is filled with air to carry out the trapping process, and the fixed bed reactor B with the trapping completed is filled with H 2 Carrying out a conversion process; the second working mode is as follows: after the chemical reactions in the fixed bed reactor A and the fixed bed reactor B reach equilibrium, the air inlet of the fixed bed reactor A and the air inlet of the fixed bed reactor B are switched through the first four-way reversing valve, the temperature of the fixed bed reactor A is changed, the temperature of the fixed bed reactor A is raised to about 300 ℃, and H is introduced 2 Finishing conversion and adsorbent regeneration, cooling the fixed bed reactor B to normal temperature, and introducing air to finish CO 2 And capturing, namely completing replacement from the first working mode to the second working mode. The hydrogen production machine in the integrated system is powered by renewable power such as photoelectricity, wind power and the like to prepare H 2 For transformation.
The adsorption and catalysis dual-function material is a core and key for realizing DAC-ICCU technology, and consists of an adsorbent, a catalyst and a carrier. The inventionAlkali metal is used as adsorbent and comprises K 2 CO 3 、Na 2 CO 3 One or more of MgO; the catalyst implements a hydroconversion process comprising one or more of Ru, ni, co, pt; the adsorbent and the catalyst are uniformly dispersed on a carrier with larger specific surface area and proper pore structure, and the contact and mass transfer process between the carrier and the gas flow are enhanced, so that the adsorption and conversion performance is further improved, and the carrier comprises Al 2 O 3 、SiO 2 、CeO 2 One or more of the following. In the double-function material, the adsorbent is marked as M, the catalyst is marked as A, the carrier is marked as S, the respective mass percentages of the components M, A, S in the double-function material are respectively x, y and z, wherein x is 0.1-0.4, y is 0.005-0.05, and z is 1-x-y. The dual-function material is prepared by an impregnation method or a one-pot method; for the impregnation method, the adsorbent and the catalyst are loaded on the carrier, and the two components are impregnated simultaneously or sequentially, namely, the adsorbent is impregnated first and then the catalyst is impregnated, or the catalyst is impregnated first and then the adsorbent is impregnated; for the one-pot method, the adsorbent, the catalyst and the carrier metal precursor salt are dissolved in deionized water together, citric acid is added as a complexing agent, the mixture is heated and stirred to form sol, then the sol is dried to obtain puffed solid, and finally the puffed solid is calcined to obtain the bifunctional material with uniformly dispersed elements. .
To utilize Ru-K 2 CO 3 -Al 2 O 3 For example, adsorbing catalytic dual-function material to realize DAC-ICCU function, ru-K 2 CO 3 -Al 2 O 3 In the adsorption catalysis dual-functional material, K 2 CO 3 Is adsorbent, ru is catalyst, is loaded on Al 2 O 3 A carrier; FIG. 2 shows the direct air CO of the dual function material 2 And (5) capturing and converting an integrated mechanism diagram. CO in air at normal temperature 2 And H is 2 O、K 2 CO 3 Generating KHCO by chemical reaction 3 The method specifically comprises the following steps: CO 2 +H 2 O+K 2 CO 3 →2KHCO 3 ，CO 2 Is trapped on the adsorbent site, after the adsorption reaches saturation, the fixed bed reactor is heated to about 300 ℃, under the action of Ru catalyst,H 2 to H atoms, then transferred from the catalytic site to the vicinity of the adsorption site, and adsorbed CO 2 Generating subsequent reaction to generate CH 4 At the same time regenerating the adsorbent to K 2 CO 3 The method specifically comprises the following steps: 2KHCO 3 +4H 2 →K 2 CO 3 +CH 4 +3H 2 O, the regenerated material can be adsorbed and converted for the next time, so that the recycling is realized.
Ru-K 2 CO 3 -Al 2 O 3 The adsorption catalysis bifunctional material is prepared by adopting an impregnation method and comprises the following specific steps:
firstly, preparing a solution of metal precursor salt according to the proportion: 0.07gK 2 CO 3 With 0.0410g RuCl 3 H 2 O was dispersed in 0.3g deionized water, followed by adding 0.43g Al to the solution 2 O 3 (the mass is calculated according to the proportion), and the materials are mixed and stirred until the water is naturally volatilized; and then drying the solid in a 100 ℃ oven for 24 hours to obtain a dry solid, grinding the dry solid, placing the dry solid in a muffle furnace, heating the dry solid to 300 ℃ at a heating rate of 5 ℃/min, calcining the dry solid for 1 hour, and finally tabletting and granulating the obtained solid material, and sieving the solid material to obtain the solid material with a particle size of 40-60 meshes.
Ru-K 2 CO 3 -Al 2 O 3 The adsorption catalysis bifunctional material is prepared by adopting a one-pot method and comprises the following specific steps:
preparing a solution of metal precursor salt according to the proportion: 0.5g KNO 3 、1.8553gAl(NO 3 ) 3 ·9H 2 O and 0.0205g RuCl 3 H 2 O was dispersed in 7.12ml deionized water, and after stirring well 1.9003g citric acid was added and stirred vigorously at 80℃until a sol-like substance was formed. Drying the sol-like substance in a 120 ℃ oven overnight to obtain a puffed solid, grinding the puffed solid into powder, placing the powder in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min, calcining for 4 hours, and finally tabletting and granulating the obtained solid material, and sieving the solid material to obtain the solid material with a particle size of 40-60 meshes.
Ru-K is prepared 2 CO 3 -Al 2 O 3 After adsorbing the catalytic bifunctional material, the material is applied to a DAC-ICCU system, and a single reactor is used for specific experimental operationThe flow is as follows:
s1, preprocessing, namely reducing RuO into Ru, so that the bifunctional material has catalytic activity: 100mg of material is placed in a fixed bed reactor, the temperature is raised to 350 ℃, 40% H is introduced 2 /N 2 (400 mL/min) and purging and activating for 1 hour;
s2, introducing pure N 2 (400 mL/min) purged until no H is detected in the effluent stream 2 ；
S3、CO 2 The trapping process comprises the following steps: 400ppm CO is introduced at normal temperature 2 /21％O 2 /N 2 (400 mL/min) of a mixture, and a certain amount of steam, for simulating air in a real environment, K in the process 2 CO 3 CO capture 2 Generating KHCO 3 Stopping ventilation after the material reaches adsorption saturation;
s4, introducing pure N 2 (400 mL/min) purging;
s5, a conversion process: the temperature of the reactor is raised to 300-350 ℃, 40% H is introduced 2 /N 2 (400 mL/min) of CO adsorbed by the catalyst Ru during the process 2 And H is 2 Obtaining a target product CH by reaction 4 And regenerating the adsorbent to K 2 CO 3 Continuous aeration to CH in reactor effluent stream 4 Concentration is lower than 100ppm;
s6, introducing pure N 2 (400 mL/min) purged until no H is detected in the effluent stream 2 。
And S7, repeating the steps S1-S6 to finish recycling, wherein the steps S1-S6 are all carried out under normal pressure.
FIG. 3 is a graph showing the concentration change of each gas component (CO 2, CH4, CO) in the adsorption and conversion stages of the Ru/K2CO3/Al2O3 bifunctional material, wherein the CO2 concentration reaches 400ppm in 100min in the capturing stage, and the adsorption is considered to be saturated; in the temperature-rising hydroconversion stage, the main product is CH4, a small amount of byproduct CO is generated, a small amount of CO2 is released, and at 45min, the concentration of CH4 is reduced to below 100ppm, so that the conversion stage is considered to be completed. The material has a CO2 capture of 0.8613mmol/g and a CO2 conversion of 70.45%.
FIG. 4 is a graph showing the concentration change of each gas component (CO 2, CH4, CO) in the adsorption and conversion stages of the Ru/Na2CO3/Al2O3 bifunctional material, wherein the adsorption saturation is reached in the trapping stage for 150min, and the conversion is completed after 37 min.
The invention realizes the capturing and conversion utilization of CO2 in the air through the adsorption and catalysis dual-function material, does not need to release, purify and store the CO2 after capturing, can directly carry out hydroconversion and utilization to prepare methane as fuel, and realizes the high-efficiency utilization of energy and the great simplification of a system.
By adopting the method, the CO2 adsorption and catalytic material with high CO2 adsorption capacity, high methane conversion rate, high cycle stability and low energy consumption can be prepared, and the preparation process is simple (impregnation method), short in growth period, high in productivity and low in cost.
The dual-functional material and the trapping and conversion integrated system prepared by the invention can realize continuous trapping of CO2 in air, and can directly regenerate the adsorbent and prepare methane by utilizing renewable electric power, thereby solving the problems of high energy consumption and complex system in CO2 releasing, separating, storing and converting processes when CO2 trapping and converting are divided into two steps.
Compared with the prior art, the invention has the advantages that: 1. the material has good thermal stability, and is integrated with capturing and conversion to directly obtain methane; without desorption of CO 2 The sealing or utilizing is carried out, and the sealing or utilizing device has no additional transportation and storage cost, and potential risks of leakage, environmental influence and the like. 2. The carbon dioxide is directly trapped from the air, so that the preparation by the impregnation method is simpler and easier to prepare; the trapping process does not need heating, and the conversion temperature is lower, so that the energy is saved; the direct air carbon capture does not need to consider the influence of pollutants in the flue gas; is not limited by region, and can be arranged near renewable power facilities directly.
Key innovation points in the invention include:
1. avoiding the defects of the traditional DAC and CO2 conversion utilization technology and providing direct air CO based on adsorption catalysis dual-function material 2 The trapping and conversion integrated (DAC-ICCU) technology is adopted, materials capable of realizing the functions are prepared, and the design of an operation system is completed;
2. preparation of double functions by impregnation methodCan be made of alkali metal carbonate K 2 CO 3 、Na 2 CO 3 The catalyst is one or more of Ru, ni, co and Pt and the carrier is Al 2 O 3 ，SiO 2 One or more of (a) and (b); by alkali metal carbonate with CO in air 2 、H 2 CO is realized by O reaction 2 Chemisorption to form alkali metal bicarbonate; then, the hydrogen carbonate is added with renewable power to produce green hydrogen for catalytic conversion to generate CH 4 Meanwhile, the regeneration of the adsorbent is realized, the adsorbent is restored to alkali carbonate, and the adsorption of the next cycle is carried out;
3. propose direct air CO 2 The trapping and conversion integrated (DAC-ICCU) double-reactor system changes the reaction mode by periodically switching the air inlet (air/hydrogen) and the temperature rise and fall of each reactor, realizes the efficient carbon trapping and conversion process, and improves the carbon dioxide trapping amount, conversion rate and methane yield of the device.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, apparatus, article, or method that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, apparatus, article, or method. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, apparatus, article or method that comprises the element.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes using the descriptions and drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the invention.
Claims (8)
1. The integrated system is characterized by comprising a fixed bed reactor A and a fixed bed reactor B, wherein one end of the fixed bed reactor A is connected with one end of the fixed bed reactor B through a first four-way reversing valve, the other end of the fixed bed reactor A is connected with the other end of the fixed bed reactor B through a second four-way reversing valve, the fixed bed reactor A and the fixed bed reactor B are filled with adsorption catalysis bifunctional materials, and the adsorption catalysis bifunctional materials are formed on the basis of alkali metal adsorbents and transition metal catalysts;
the fixed bed reactor A and the fixed bed reactor B are periodically switched by two working modes to realize circulation, and the first working mode is as follows: the fixed bed reactor A is filled with air to carry out the trapping process, and the fixed bed reactor B with the trapping completed is filled with H 2 Carrying out a conversion process; the second working mode is as follows: after the chemical reactions in the fixed bed reactor A and the fixed bed reactor B reach equilibrium, the air inlet of the fixed bed reactor A and the air inlet of the fixed bed reactor B are switched through the first four-way reversing valve, the temperature of the fixed bed reactor A is changed, the temperature of the fixed bed reactor A is raised to about 300 ℃, and H is introduced 2 Finishing conversion and adsorbent regeneration, cooling the fixed bed reactor B to normal temperature, and introducing air to finish CO 2 And capturing, namely completing replacement from the first working mode to the second working mode.
2. The dual function material adsorption catalyst system for carbon dioxide capture of claim 1, wherein the H 2 Produced by a hydrogen production machine powered by renewable electricity to produce H 2 The renewable power comprises photoelectrical power and wind power.
3. The integrated system for capturing and converting based on carbon dioxide adsorption catalysis dual-function material as claimed in claim 1, wherein the adsorption catalysis dual-function material is composed of an adsorbent, a catalyst and a carrier, and the adsorbent adopts alkali metal and comprises K 2 CO 3 、Na 2 CO 3 One or more of MgO, the catalyst realizes a hydroconversion process and comprises one or more of Ru, ni, co, pt, and the carrier comprises Al 2 O 3 、SiO 2 、CeO 2 One or more of (a) and (b);
the adsorbent and catalyst are uniformly dispersed on a carrier having a set specific surface area and pore structure to enhance the contact and mass transfer process with the gas stream.
4. The integrated system for capturing and converting based on a carbon dioxide adsorbing and catalyzing dual-function material according to claim 3, wherein the adsorbent is denoted as M, the catalyst is denoted as a, the carrier is denoted as S, the respective mass percentages of the component M, A, S in the adsorbing and catalyzing dual-function material are x, y and z, wherein x is 0.1-0.4, y is 0.005-0.05, and z is 1-x-y.
5. The integrated system for capturing and converting based on the carbon dioxide adsorption catalysis bifunctional material of claim 4, wherein the adsorption catalysis bifunctional material is prepared by an impregnation method or a one-pot method; for the impregnation method, the adsorbent and the catalyst are loaded on the carrier, and the two components are impregnated simultaneously or sequentially, namely, the adsorbent is impregnated first and then the catalyst is impregnated, or the catalyst is impregnated first and then the adsorbent is impregnated; for the one-pot method, the adsorbent, the catalyst and the carrier metal precursor salt are dissolved in deionized water together, citric acid is added as a complexing agent, the mixture is heated and stirred to form sol, then the sol is dried to obtain puffed solid, and finally the puffed solid is calcined to obtain the bifunctional material with uniformly dispersed elements.
6. The integrated system for capturing and converting based on carbon dioxide adsorption catalysis dual-function material according to claim 5, wherein Ru-K is adopted 2 CO 3 -Al 2 O 3 As the adsorption-catalysis dual-function material, wherein K 2 CO 3 Is adsorbent, ru is catalyst, is loaded on Al 2 O 3 A carrier;
Ru-K 2 CO 3 -Al 2 O 3 direct air CO adsorbing catalytic double function material 2 The trapping and conversion integrated mechanism mode is as follows: at the normal temperature, the temperature of the mixture is higher than the temperature of the mixture,CO in air 2 And H is 2 O、K 2 CO 3 Generating KHCO by chemical reaction 3 The method specifically comprises the following steps: CO 2 +H 2 O+K 2 CO 3 →2KHCO 3 ，CO 2 Is trapped on the adsorbent site, after the adsorption reaches saturation, the fixed bed reactor A is heated to about 300 ℃, under the action of Ru catalyst, H 2 To H atoms, then transferred from the catalytic site to the vicinity of the adsorption site, and adsorbed CO 2 Generating subsequent reaction to generate CH 4 At the same time regenerating the adsorbent to K 2 CO 3 The method specifically comprises the following steps: 2KHCO 3 +4H 2 →K 2 CO 3 +CH 4 +3H 2 O, the regenerated material can be adsorbed and converted for the next time, so that the recycling is realized.
7. The integrated system for capturing and converting based on carbon dioxide adsorption catalysis dual-function material according to claim 6, wherein Ru-K 2 CO 3 -Al 2 O 3 The adsorption catalysis bifunctional material is prepared by adopting an impregnation method and comprises the following specific steps:
preparing a solution of metal precursor salt according to the proportion: 0.07gK 2 CO 3 With 0.0410g RuCl 3 H 2 O was dispersed in 0.3g deionized water, followed by adding 0.43g Al to the solution 2 O 3 Wherein Al is 2 O 3 The mass of the water is obtained according to the proportion calculation, and the water is mixed and stirred until the water is naturally volatilized; and then drying the solid in a 100 ℃ oven for 24 hours to obtain a dry solid, grinding the dry solid, placing the dry solid in a muffle furnace, heating the dry solid to 300 ℃ at a heating rate of 5 ℃/min, calcining the dry solid for 1 hour, and finally tabletting and granulating the obtained solid material, and sieving the solid material to obtain the solid material with a particle size of 40-60 meshes.
8. The integrated system for capturing and converting carbon dioxide adsorption catalysis-based bifunctional material of claim 7, wherein Ru-K is prepared by 2 CO 3 -Al 2 O 3 The specific experimental operation flow of the adsorption catalysis bifunctional material applied to a single fixed bed reactor is as follows:
s1, preprocessing, namely reducing RuO into Ru, so that the bifunctional material has catalytic activity: 100mg of material is placed in a fixed bed reactor, the temperature is raised to 350 ℃, 40% H is introduced 2 /N 2 The mixture is purged and activated for 1 hour;
s2, introducing pure N 2 Purging until no H is detected in the effluent stream 2 ；
S3、CO 2 The trapping process comprises the following steps: 400ppm CO is introduced at normal temperature 2 /21％O 2 /N 2 A mixture of gases, and a set amount of water vapor for simulating air in a real environment, K in the process 2 CO 3 CO capture 2 Generating KHCO 3 Stopping ventilation after the material reaches adsorption saturation;
s4, introducing pure N 2 Purging;
s5, a conversion process: heating the fixed bed reactor to 300-350 ℃, and introducing 40% H 2 /N 2 Mixture gas, CO adsorbed under the action of Ru catalyst 2 And H is 2 Obtaining a target product CH by reaction 4 And regenerating the adsorbent to K 2 CO 3 Continuous aeration to CH in reactor effluent stream 4 Concentration is lower than 100ppm;
s6, introducing pure N 2 Purging until no H is detected in the effluent stream 2 ；
And S7, repeating the steps S1-S6 to finish recycling, wherein the steps S1-S6 are all carried out under normal pressure.
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