CN117504577A - Preparation method of CaO-based dual-function material, caO-based dual-function material and application thereof - Google Patents
Preparation method of CaO-based dual-function material, caO-based dual-function material and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 239000002184 metal Substances 0.000 claims abstract description 54
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 26
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 22
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000004471 Glycine Substances 0.000 claims abstract description 11
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 11
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 238000003980 solgel method Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- -1 organic acid salt Chemical class 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 3
- 230000000996 additive effect Effects 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 15
- 238000011065 in-situ storage Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
Abstract
The invention discloses a preparation method of a CaO-based bifunctional material, the CaO-based bifunctional material and application thereof. The preparation method comprises the steps of adopting a dipping, hydrothermal synthesis or sol-gel method to blend or react a carbon capture metal precursor, a catalyst metal precursor, an auxiliary metal precursor, xylose, glycine and urea to form a mixture; and calcining the mixture in air at 400-900 ℃ for 2-6 hours to obtain the CaO-based dual-function material. The invention has CO 2 The advantages of high adsorption capacity and high conversion rate are that the trapping time can be basically leveled, thereby realizing the high-efficiency and convenient ICCU-methanation.
Description
Technical Field
The present invention relates to CO 2 The technical field of trapping/conversion, in particular to a preparation method of a CaO-based bifunctional material and the CaO-based bifunctional material.
Background
Carbon Capture Utilization and Sequestration (CCUS) technology is one of the necessary technical means for long-term global warming containment, but has hampered the practical industrial application of CCUS due to the drawbacks of high cost and energy consumption penalty. In order to reduce the cost and energy consumption caused by large-scale application resistance, the Integrated Carbon Capture and Utilization (ICCU) technology is based on CCUSIt was proposed to use Dual Function Materials (DFM) to discharge CO in the same reactor 2 The waste gas is captured and directly converted into value added chemical products or fuels, thereby reducing the cost and energy consumption of the CCUS in the processes of purification, compression, storage and intermediate transportation.
Currently, ICCU is mainly through the following COs 2 The conversion pathway captures CO 2 Directly into the corresponding carbon compound, as shown in the formula (1-5). From the formulae (1-5), methanation in the formula (1) is the only exothermic reaction therein. With other CO 2 Compared to shift reactions, methanation may provide adsorbent desorption of CO 2 The heat required reduces the energy supply. For the current CO 2 The maximum energy consumption of the adsorbent comes from the CO 2 The energy required for desorption, while other CO 2 The transformation pathway undoubtedly aggravates CO 2 The energy required for the desorption and in situ conversion stages is in particular the CaO adsorbent widely used in ICCU (formula 6).
CO 2 +4H 2 →CH 4 +2H 2 O，ΔH (r，298K) ＝-164kJ·mol -1 (1)
CO 2 +H 2 →CO+H 2 O，ΔH (r，298K) ＝+41.2kJ·mol -1 (2)
CO 2 +CH 4 →2CO+2H 2 ，ΔH (r，298K) ＝+247kJ·mol -1 (3)
2CO 2 +C 2 H 6 →4CO+3H 2 ，ΔH (r，298K) ＝+428.1kJ·mol -1 (4)
CO 2 +C 2 H 6 →C 2 H 4 +CO+H 2 O，ΔH (r298K) ＝+149kJ·mol -1 (5)
CaCO 3 →CO 2 +CaO，H 298K ＝+178kJ·mol -1 (6)
At the same time ICCU-methanation provides another hydrogen storage process, which is a very attractive "electric conversion" technology. Thus, ICCU-methanation clearly has the most widely applicable potential in terms of cost and energy consumption as hydrogen technology evolves.
Ideally, when the in situ conversion time is close to CO 2 When the trapping time is reached, two reaction devices can be alternatively used to complete continuous CO of industrial waste gas 2 Trapping and in situ conversion. CaO adsorbent has low cost and CO 2 Large capacity, but limited by low operating temperature, CO when CaO matches ICCU methanation reaction temperature 2 The desorption reaction kinetics is slow. The in situ conversion time is far longer than that of CO 2 Capture time, resulting in the need to add multiple reaction units to balance CO in practical applications 2 Capture time and in situ conversion time. This not only increases construction costs, but also increases equipment space volume and operational complexity.
Therefore, there is a need for improvements in CaO-based adsorbents that absorb and desorb CO at low temperatures 2 To achieve efficient and convenient ICCU-methanation.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a preparation method of a CaO-based bifunctional material, the CaO-based bifunctional material and application thereof, and the CaO-based bifunctional material has CO 2 The advantages of high adsorption capacity and high conversion rate are that the trapping time can be basically leveled, thereby realizing the high-efficiency and convenient ICCU-methanation.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of CaO-based dual-function material comprises,
blending or reacting a carbon capture metal precursor, a catalyst metal precursor, an auxiliary metal precursor, xylose, glycine and urea to obtain a mixture;
calcining the mixture in air at 400-900 ℃ for 2-6 hours to obtain the CaO-based dual-function material;
wherein, the molar ratio of the carbon capture metal precursor, the catalyst metal precursor, the auxiliary metal precursor, the xylose, the glycine and the urea is (80-95): (1-10): (2.5-10): (80-240): (10-70): (30-210).
Preferably, the carbon-trapping metal precursor includes a nitrate or a soluble organic acid salt containing Ca.
In specific implementation, the catalyst metal precursor is nitrate or soluble organic acid salt containing catalytic metal elements.
Preferably, the catalytic metal element includes Ni or Ru.
In particular embodiments, the promoter metal precursor includes a nitrate or soluble organic acid salt containing a promoter metal element.
Preferably, the auxiliary metal element comprises Ti, zr, cr, zn, V or W.
In specific implementation, the mixture is prepared by adopting a dipping method, a hydrothermal synthesis method or a sol-gel method.
Preferably, the preparation of the mixture by adopting a hydrothermal synthesis method comprises the steps of uniformly mixing a carbon capture metal precursor, a catalyst metal precursor, an auxiliary metal precursor, xylose, glycine and urea, completely dissolving in deionized water, preserving at 100-200 ℃ for 24-72 hours, washing and drying to obtain the mixture.
The invention also discloses a CaO-based bifunctional material, which is characterized in that the CaO-based bifunctional material is prepared by adopting the preparation method of the CaO-based bifunctional material.
The invention also discloses application of the CaO-based bifunctional material, which is used for CO 2 Is captured and converted.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the CaO-based dual-function material provided by the invention adopts a dipping, hydrothermal synthesis or sol-gel method to blend or react a carbon capture metal precursor, a catalyst metal precursor, an auxiliary metal precursor, xylose, glycine and urea to form a mixture, and then the mixture is calcined to obtain the CaO-based dual-function material. The method has simple steps and is easy to operate.
2. The CaO-based dual-function material provided by the invention has the advantages that as the acidic metal oxide is added as the auxiliary agent,the adsorption and activity of H are enhanced, so that the H can react with carbonate more easily, and the reaction rate is accelerated. The CaO-based dual-function material is used for preparing CO 2 Adsorption amount of more than 48wt.%, with CO 2 The adsorption capacity is high; the highest methane generation rate is 1.3mmol/min, which is 6 times of the traditional Ni/CaO conversion rate, and the trapping time can be basically leveled; five times CO 2 Adsorption performance is not attenuated after the trapping/methanation integrated process, and CO 2 The conversion rate is higher than 99%, the methane selectivity is higher than 99%, and the method has the advantages of rapid and stable cyclic adsorption-desorption/in-situ conversion performance, high conversion rate, good product selectivity and the like. In addition, the CaO-based dual-function material has low CO 2 Still has higher CO at the concentration 2 The adsorption capacity can meet the industrial application requirements.
Drawings
FIG. 1 is a flow chart of a hydrothermal method for preparing CaO-based dual-function materials in an embodiment of the invention.
Fig. 2 is a scan of the bifunctional material prepared in example 1 of the present invention.
Fig. 3 is a scan of the bifunctional material prepared in comparative example 1.
Fig. 4 is a scan of the bifunctional material prepared in comparative example 2.
Fig. 5 is a scan of the bifunctional material prepared in comparative example 3.
FIG. 6 shows the preparation of a bifunctional material CO in example 1 and comparative examples 1 to 3 of the present invention 2 And a trapping/methanation integrated performance test chart.
FIG. 7 is a graph showing the CO at 550℃of the bifunctional material prepared in example 1 of the present invention 2 Carbon capture amount cycle chart at the time of capture/methanation integration.
FIG. 8 is a graph showing the ICCU-methanation reaction of the bifunctional material 2 prepared in example 2 at 600 ℃.
FIG. 9 shows the bifunctional material 1 prepared in example 1, the bifunctional material 2 prepared in example 2, and the pair 1 NH pair prepared in comparative example 1 3 Is drawn from the figure.
FIG. 10 is a graph comparing ICCU-methanation performance at 600℃of the bifunctional material 1 prepared in example 1 and the bifunctional materials 3-5 prepared in examples 3-5.
Detailed Description
The embodiment of the invention discloses a preparation method of CaO-based dual-function material, which comprises the following steps,
blending or reacting a carbon capture metal precursor, a catalyst metal precursor, an auxiliary metal precursor, xylose, glycine and urea to obtain a mixture;
calcining the mixture in air at 400-900 ℃ for 2-6 hours to obtain the CaO-based dual-function material;
wherein, the molar ratio of the carbon capture metal precursor, the catalyst metal precursor, the auxiliary metal precursor, the xylose, the glycine and the urea is (80-95): (1-10): (2.5-10): (80-240): (10-70): (30-210).
The embodiment of the invention also discloses a CaO-based dual-function material, which is characterized in that the CaO-based dual-function material is prepared by adopting the preparation method of the CaO-based dual-function material.
The embodiment of the invention also discloses an application of the CaO-based bifunctional material, which is used for CO 2 Is captured and converted.
1. Preparation of bifunctional materials
Example 1
This example uses hydrothermal synthesis to prepare a mixture, the preparation scheme of which is shown in FIG. 1. Weighing carbon-trapping metal precursor Ca (NO) 3 ) 2 ·4H 2 O, catalyst metal precursor Ni (NO 3 ) 2 ·6H 2 O, adjuvant metal precursor Zr (NO) 3 ) 4 ·5H 2 Powder materials of O, xylose, glycine and urea, 54.4mmol, 6.8mmol, 160mmol, 26.4mmol and 72mmol respectively, and 100mL of deionized water was added until the blend was completely dissolved. Transferring the solution into a stainless steel autoclave lined with polytetrafluoroethylene, performing hydrothermal reaction at 180 ℃ for 24 hours, cooling to room temperature, repeatedly washing and filtering a hydrothermal sample by using absolute ethyl alcohol and deionized water, and putting into an oven at 80 ℃ for drying to obtain a mixture. Calcining the mixture at 700 ℃ for 6 hours to obtain the CaO-based dual-function material, which is named as dualFunctional material 1. A scan of the bifunctional material prepared in this example is shown in fig. 2. As can be seen from FIG. 2, the CaO-based bifunctional material has a prismatic structure, and the successful loading of Zr and Ni elements on CaO is further proved by an element scanning graph.
Comparative example 1
The bifunctional material prepared in this comparative example is different from example 1 in that, in the preparation process, carbon-trapped metal precursor Ca (NO 3 ) 2 ·4H 2 O is 61.2mmol, and NO auxiliary metal precursor Zr (NO) 3 ) 4 ·5H 2 O, the remainder of which was the same as in example 1 and designated as pair 1.
A scan of the dual-function material prepared in comparative example 1 is shown in fig. 3, and as can be seen from fig. 3, the material exhibits a spheroid-like structure, and further, successful loading of Ni element on CaO is demonstrated by the element scan.
Comparative example 2
The bifunctional material prepared in this comparative example is different from example 1 in that, during the preparation, an auxiliary metal precursor Zr (NO 3 ) 4 ·5H 2 O is replaced by Ce (NO) 3 ) 3 ·4H 2 O, the number of moles of which was unchanged, was designated as pair 2 in the same manner as in example 1.
A scan of the dual-function material prepared in comparative example 2 is shown in fig. 4, and as can be seen from fig. 4, the material presents a multi-sphere polymeric structure, and further, successful loading of Ce and Ni elements on CaO is proved by an element scan.
Comparative example 3
The bifunctional material prepared in this comparative example is different from example 1 in that, during the preparation, an auxiliary metal precursor Zr (NO 3 ) 4 ·5H 2 O is replaced by Mg (NO) 3 ) 2 ·6H 2 O, the number of moles of which was unchanged, was designated as pair 3 in the same manner as in example 1.
Referring to fig. 5, it can be seen from fig. 5 that the functional material-3 has a prismatic structure, and further, the successful loading of Mg and Ni elements on CaO is demonstrated by the element scan.
Example 2
The CaO-based dual-function material adopts a dipping method, and the specific preparation method comprises the following steps:
54.4mmol of nano calcium carbonate and 6.8mmol of Zr (NO) were weighed out 3 ) 4 ·5H 2 O was placed in a 100mL beaker, and 10mL of ionized water was added to dissolve Zr (NO) 3 ) 4 ·5H 2 After O, the mixture was stirred in a water bath at 80℃until the water in the beaker had evaporated completely, allowing Zr (NO 3 ) 4 ·5H 2 O is precipitated on the nano calcium carbonate. Then the mixture is put into a crucible, and the crucible is put into a muffle furnace to be heated to 550 ℃ in air and kept for 5 hours, and then cooled to room temperature, so as to obtain a calcined powder sample. The calcined powder sample was combined with 6.8mmol Ni (NO 3 ) 2 ·6H 2 O was placed in a 100mL beaker, and 10mL of ionized water was added to dissolve Zr (NO) 3 ) 4 ·5H 2 O, stirring in a water bath at 80deg.C until the water in the beaker is completely evaporated, to dissolve Ni (NO 3 ) 2 ·6H 2 And (3) depositing O on the calcined powder sample, finally loading the powder sample into a crucible, putting the crucible into a muffle furnace, heating the crucible to 550 ℃ in the air, preserving the heat for 5 hours, cooling the crucible to room temperature, and taking out the sample to obtain the CaO-based dual-function material, namely the dual-function material 2.
Examples 3 to 5
The preparation method of the bifunctional materials in examples 3 to 5 is the same as that of example 1, and the composition and the proportion thereof are shown in Table 1 and are respectively designated as bifunctional material 3, bifunctional material 4 and bifunctional material 5.
Table 1 the ingredients and proportions of the bifunctional materials prepared in examples 3 to 5, mol.%
| Trapping metal oxides | Auxiliary metal | Catalytic metal | |
| Example 3 | 85mol.％CaO | 5mol.％ZrO 2 | 10mol.％Ni |
| Example 4 | 87.5mol.％CaO | 2.5mol.％ZrO 2 | 10mol.％Ni |
| Example 5 | 89mol.％CaO | 1mol.％ZrO 2 | 10mol.％Ni |
2. Performance testing
CO was performed on the bifunctional material 1 prepared in example 1 and the pairs 1 to 3 prepared in comparative examples 1 to 3 2 Trapping/methanation integrated performance test, wherein the operation temperature is 550 ℃, and 15vol.% CO is introduced in the first 30min 2 /N 2 The mixed gas of (2) simulates the flue gas to carry out carbon capture, and the introduced gas is changed into pure H after the carbon capture 2 And performing in-situ methanation reaction. The test results are shown in fig. 6.
As is clear from FIG. 6 (a), the methanation of 1 (i.e., ni alone) was completed for 150 minutes or more, and the maximum conversion rate was 0.26mmol/min. When other metals are added, as shown in FIG. (c) for 2 (i.e., ceO 2 CaO bifunctional material) and 3 (i.e., mgO/CaO bifunctional material) in the graph (d), the in-situ conversion rate can be effectively improved to a certain extent by increasing the dispersibility of CaO by reducing the specific gravity of CaO, while methanation is completedThe time is still more than 80min, and the highest conversion rate is about 0.44 mmol/min. To which acidic metal oxides (ZrO 2 ) The methanation of the difunctional material 1 serving as the auxiliary agent is completed within 40min, and as shown in (b), the highest conversion rate is 1.3mmol/min, which is 5 times of the conversion rate of the traditional Ni/CaO, so that the trapping time can be basically leveled, and the trapping and conversion integration can be completed better.
The bifunctional material 1 prepared in example 1 was subjected to CO at 550 ℃ 2 The carbon capture amount cycle at the time of capture/methanation integration is shown in fig. 7. As can be seen from fig. 7, in the actual simulated flue gas containing water vapor and oxygen, the CaO-based dual-function material maintains good carbon capture cycle performance, and can meet the actual industrial application requirements.
The reaction curve of ICCU-methanation at 600℃for the bifunctional material 2 prepared in example 2 is shown in FIG. 8. Bifunctional material 1, bifunctional material 2, and NH of comparative example 1 3 Adsorption is shown in fig. 9. From FIGS. 8 and 9, it can be seen that the addition of the acid metal is critical to the change in the in situ methanation rate. The acid strength obtained by different preparation methods aiming at the same acid metal oxide is different, and the methanation rate is different. The more acidic the faster the methanation rate.
The pair of ICCU-methanation properties of the bifunctional material 1 prepared in example 1 and the bifunctional materials prepared in examples 3 to 5 at 600℃are shown in FIG. 10. As can be seen from FIG. 10, with ZrO 2 An increase in the content, a significant increase in the methanation rate up to ZrO 2 The content reaches 5mol.%, the methanation rate starts to remain unchanged.
Therefore, the CaO-based dual-function material provided by the embodiment of the invention is used for CO 2 Adsorption amount of more than 48wt.%, with CO 2 The adsorption capacity is high; the highest conversion rate is 1.3mmol/min, which is 5 times of the conversion rate of the traditional Ni/CaO, and the capturing time can be basically leveled; five times CO 2 Adsorption performance is not attenuated after the trapping/methanation integrated process, and CO 2 The conversion rate is higher than 99%, the methane selectivity is higher than 99%, and the method has the advantages of rapid and stable cyclic adsorption-desorption/in-situ conversion performance, high conversion rate, good product selectivity and the like. In addition, the CaO-based unitDual function materials at low CO 2 Still has higher CO at the concentration 2 The adsorption capacity can meet the industrial application requirements.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. A preparation method of CaO-based dual-function material is characterized by comprising the following steps of,
blending or reacting a carbon capture metal precursor, a catalyst metal precursor, an auxiliary metal precursor, xylose, glycine and urea to obtain a mixture;
calcining the mixture in air at 400-900 ℃ for 2-6 hours to obtain the CaO-based dual-function material;
wherein, the molar ratio of the carbon capture metal precursor, the catalyst metal precursor, the auxiliary metal precursor, the xylose, the glycine and the urea is (80-95): (1-10): (2.5-10): (80-240): (10-70): (30-210).
2. The method of producing CaO-based dual function material according to claim 1, characterized in that the carbon capture metal precursor includes a nitrate or soluble organic acid salt containing Ca.
3. The method for producing CaO-based bifunctional material according to claim 1, characterized in that the catalyst metal precursor is a nitrate or a soluble organic acid salt containing a catalytic metal element.
4. A method of preparing a CaO-based bifunctional material as recited in claim 3 wherein the catalytic metal element comprises Ni or Ru.
5. The method for producing CaO-based dual function material according to claim 1, characterized in that the additive metal precursor includes nitrate or soluble organic acid salt containing additive metal element.
6. The method for producing a CaO-based dual function material according to claim 5, characterized in that the additive metal element is Zr, cr, zn, V or W.
7. The method for preparing the CaO-based dual function material according to claim 1, wherein the mixture is prepared by a dipping method, a hydrothermal synthesis method or a sol-gel method.
8. The method for preparing the CaO-based dual-function material according to claim 1, wherein preparing the mixture by a hydrothermal synthesis method includes uniformly mixing a carbon-trapping metal precursor, a catalyst metal precursor, an auxiliary metal precursor, xylose, glycine and urea, completely dissolving the mixture in deionized water, preserving the mixture at 100-200 ℃ for 24-72 hours, washing and drying the mixture, and obtaining the mixture.
9. A CaO-based bifunctional material, wherein the CaO-based bifunctional material is prepared by a method for preparing a CaO-based bifunctional material according to any one of claims 1 to 8.
10. Use of a CaO-based bifunctional material as defined in claim 8 for CO 2 Is captured and converted.
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