CN116588935A - Method for reducing CO2 by coupling low-temperature plasma with bismuth-based MOF catalyst - Google Patents
Method for reducing CO2 by coupling low-temperature plasma with bismuth-based MOF catalyst Download PDFInfo
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- 239000012918 MOF catalyst Substances 0.000 title claims abstract description 41
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 19
- 230000008878 coupling Effects 0.000 title claims abstract description 11
- 238000010168 coupling process Methods 0.000 title claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000006004 Quartz sand Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 230000004888 barrier function Effects 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 210000002381 plasma Anatomy 0.000 description 54
- 239000003054 catalyst Substances 0.000 description 20
- 238000006722 reduction reaction Methods 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000009919 sequestration Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical class [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/54—Bismuth
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a low-temperature plasma coupling bismuth-based MOF catalyst for reducing CO 2 Dispersing bismuth nitrate pentahydrate and an organic ligand in an organic solvent, magnetically stirring and mixing to obtain an emulsion, placing the emulsion in a closed high-pressure reaction kettle for reaction to obtain a mixture with solid and liquid, filtering the solid in the mixture, washing the mixture for a plurality of times by the organic solvent to remove residues on the surface of the solid, and drying the washed solid in an oven to obtain the Bi-MOF catalyst; filling a Bi-MOF catalyst and quartz sand in a discharge area of a low-temperature plasma reactor, and then introducing a gas-phase oxidant into the low-temperature plasma reactor; the discharge condition of dielectric barrier discharge of the low-temperature plasma reactor is regulated to start discharging, so that the gas phase oxidant carries out catalytic reaction on the surface of the Bi-MOF and quartz sand to generate CO, and CO and other tail gases pass through the gas of the low-temperature plasma reactorThe outlet is discharged out of the reactor.
Description
Technical Field
The invention relates to a low-temperature plasma coupling bismuth-based MOF catalyst for reducing CO 2 Is a method of (2).
Background
At present to CO 2 Geological sequestration, immobilization and chemical conversion are performed by collecting and utilizing CO 2 Due to geological sequestration and fixation of CO 2 Is costly and may be potentially harmful to the environment, but is CO 2 The chemical conversion is convenient, effective and environment-friendly, and is paid attention to and paid attention to all nationwide students. Wherein CO 2 Is converted by CO 2 And (3) producing chemicals with higher added values for raw materials. Most of the carbon dioxide is converted to urea, inorganic carbonates and pigments, but only small amounts of carbon dioxide are converted to other high value-added chemicals. Wherein, CO is an important chemical raw material for synthesizing organic acid, aldehyde and alcohol, which represents higher added value, thus CO 2 Direct conversion to CO and O 2 And have attracted extensive attention. In addition, CO is also a key C1 feedstock in the fischer-tropsch process and can be used for the synthesis of petroleum and oxygenates. CO is processed by 2 The carbon dioxide is decomposed into CO, so that the carbon dioxide is reasonably utilized, the greenhouse effect is controlled, and the pressure of global energy crisis is relieved.
Due to CO 2 The molecular structure is stable, and higher energy input is required for breaking C=O (750 kJ/mol), which also affects CO 2 The main obstacle to effective utilization. CO 2 The traditional method of transformation is pyrolysis method, but the method has high energy consumption and low energy efficiency, and CO and O are processed at high temperature 2 It is difficult to separate and cause explosion easily, and thus, it is difficult to apply to large-scale industrial production. Photocatalytic, electrocatalytic and photoelectric reduction of CO by students at home and abroad in recent years 2 The technology is researched, but the methods still have certain limitations, including problems of low reaction rate, more byproducts, poor catalyst activity and the like. Constructing reaction systems of different media, selecting and optimizing proper catalysts to improve CO 2 The stability and efficiency of the reaction during the transformation process will be the key research direction in the field in the future.
However, CO is converted in the plasma 2 In the process of the method, the problems of low energy efficiency and the like in the reaction process still exist, the addition of the catalyst is favorable for the directional and efficient conversion of reactants, and the regulation and the optimization of the reaction process can be realized by combining the plasma and the catalysis technology.
According to the previous research results and related reports, the selection and design of an excellent catalyst are key problems to be solved by the plasma coupling catalysis technology. The designed catalytic material firstly can be fully matched with the characteristics of plasma, and secondly is suitable for the complex conditions of sintering flue gas and the characteristics of pollutants.
Since the plasma is rich in high-energy electrons, active free radicals and O 3 The design thought of the catalyst reported in the prior art mainly aims at improving the reaction rate of the catalyst on O 3 The decomposition and utilization of the catalyst, the improvement of the surface active oxygen content of the catalyst, the influence of the physical property of the catalyst on the plasma discharge form and the like, but the problems of high energy consumption, incomplete degradation and the like still exist to a certain extent. And the high-energy electrons are used as core species of the plasma, so that the catalyst capable of effectively utilizing the high-energy electrons is designed to improve the utilization rate of the plasma and related mechanisms are fewer. Therefore, it is necessary to develop a novel catalyst that sufficiently matches the characteristics of plasma and to explore the activation mode and the coupling mechanism of the catalyst and plasma.
It has been found that after metal-organic frameworks (MOFs) obtain certain energy, conjugated pi bonds are prolonged to cause delocalization of orbits, which can show the characteristics of semiconductors, and the energy of high-energy electrons in low-temperature plasmas can reach 1-20 e V, so that the energy required by semiconductor activation can be completely covered, and therefore, when the high-energy electrons collide with a catalyst, enough energy can be provided for the catalyst to activate the catalyst, and new active free radicals are generated to promote the degradation of pollutants; in addition, MOFs have large specific surface area, and the subject group has proved that the MOFs have excellent adsorption performance on chlorinated organic compounds and mercury, so that the residence time of the MOFs in a discharge area can be effectively prolonged, and the treatment efficiency is improved. Besides good adsorption performance on pollutants, MOFs are expected to form microporous discharge in plasma due to the unique porous characteristic of MOFs, so that the discharge intensity is enhanced, and the MOFs are good choices of a plasma catalytic system.
The bismuth metal has good catalytic activity, is less toxic and harmless, so that the bismuth complex is commonly used for green catalysts and has relatively low price. Bi-MOFs have high stability, repeatability and good catalytic activity, and besides being used as a catalyst, the Bi-MOFs can be used in the aspect of fluorescence by virtue of the good chemical and thermal stability and the luminous characteristic of an internal ligand, and the bismuth-based catalyst can reduce carbon dioxide into formic acid, carbon monoxide, methane and the like under the (photo) electrocatalytic condition. It also has proven to have good antibacterial properties and can be used in the fields of medicine and biology, but related studies are not yet mature enough.
However, due to the lack of large amounts of reactive oxygen species, it is difficult to make CO using a catalyst 2 Is completely reduced, thereby leading to CO 2 It is difficult to achieve higher yields. Filling a mixture of a Bi-MOF catalyst and quartz sand in a discharge area of dielectric barrier discharge, and constructing an experimental system of a low-temperature plasma coupling bismuth-based MOF catalyst for catalytic reduction of CO 2 CO can be prepared by utilizing active oxygen species generated by plasma 2 The properties of the catalyst can also be used to increase the CO yield and the energy density of the plasma.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a low-temperature plasma coupling bismuth-based MOF catalyst for reducing CO 2 Is a method of (2).
The invention adopts the technical scheme that:
CO reduction by low-temperature plasma coupling bismuth-based MOF catalyst 2 Comprises the following steps:
1) Preparation of Bi-MOF catalyst:
dispersing 150mg of bismuth nitrate pentahydrate and 750mg of organic ligand in 60ml of organic solvent, magnetically stirring and mixing to obtain emulsion, placing the emulsion in a closed high-pressure reaction kettle for reaction to obtain a mixture with solid and liquid, filtering the solid in the mixture, washing the mixture for multiple times by the organic solvent to remove residues on the surface of the solid, and placing the washed solid in an oven for drying to obtain a metal organic framework compound-Bi-MOF catalyst;
2) Reduction of CO 2 ：
Filling the Bi-MOF catalyst prepared in the step 1) and quartz sand into a discharge area of a low-temperature plasma reactor, and then introducing a gas-phase oxidant into the reactor at a gas inlet of the low-temperature plasma reactor; and then, adjusting the discharge condition of dielectric barrier discharge of the low-temperature plasma reactor to start discharge, so that the gas-phase oxidant is subjected to catalytic reaction on the surface of the Bi-MOF and quartz sand to generate CO, and the CO and other tail gases are discharged out of the reactor through a gas outlet of the low-temperature plasma reactor.
Further, in step 1):
the organic ligand adopts one of trimesic acid and phthalic acid or both;
the organic solvent is methanol or anhydrous methanol.
Further, the gas phase oxidant is CO 2 ，CO 2 95vt% -100vt% of the total gas volume in the low temperature plasma reactor; CO 2 The total flow rate of (2) was 30ml/min.
Further, the space velocity of the medium barrier discharge reaction zone of the gas-phase oxidant in the low-temperature plasma reactor is 50000-100000h -1 。
Further, in step 1): the magnetic stirring and mixing time is at least 30min;
placing the emulsion in a closed high-pressure reaction kettle, and reacting for 24 hours at 120 ℃ to obtain a mixture with solid and liquid;
the solid after standing and filtering is dried in an oven at 60-80 ℃ for 1-5h.
Further, the total mass of the Bi-MOF catalyst and quartz sand filled in the discharge region of the low temperature plasma reactor was 4g.
Further, the low-temperature plasma reactor is a coaxial cylindrical DBD reactor, the length of a discharge area of the low-temperature plasma reactor is 50mm, and the discharge power range is 20-60w.
The invention has the following beneficial effects:
1) The invention develops the novel high-efficiency stable bismuth-based MOFs material which can fully utilize high-energy electrons in the plasma through a reasonable process; on the one hand, the high-energy electrons in the plasma are utilized for CO 2 Performing the initial stageStep degradation, on the other hand, through high-efficiency catalytic materials, CO is strengthened 2 And the removal efficiency of the product CO.
2) The invention can overcome the thermodynamic reaction barrier at normal temperature and normal pressure and realize CO under mild conditions 2 Has strong reaction activity, quick reaction speed, low price, simple and convenient operation and good development prospect.
Drawings
FIG. 1 is a schematic diagram of the low temperature plasma coupled bismuth based MOF reduction of CO in accordance with the present invention 2 Schematic of the application (DBD co-catalysis);
FIG. 2 shows the low temperature plasma reduction of CO in the empty pipe condition of the present invention 2 Performance study plots;
FIG. 3 shows the CO reduction by low temperature plasma in combination with quartz sand according to the invention 2 Performance study plots;
FIG. 4 is a graph showing the CO reduction by the low temperature plasma of the present invention in combination with a 50mg Bi-MOF catalyst and quartz sand mixture 2 Performance study plots;
FIG. 5 is a graph showing the CO reduction by the low temperature plasma of the present invention in combination with a 100mg Bi-MOF catalyst and quartz sand mixture 2 Performance study plots;
FIG. 6 is a graph showing the CO reduction by the low temperature plasma of the present invention in combination with a 200mg Bi-MOF catalyst and quartz sand mixture 2 Performance study plots;
FIG. 7 shows the reduction of CO by low temperature plasma under five conditions of the present invention 2 Is a comparative study of the conversion rate of (2);
FIG. 8 shows the reduction of CO by low temperature plasma under five conditions of the present invention 2 Is a graph of energy efficiency comparison study;
FIG. 9 shows the reduction of CO by low temperature plasma under five conditions of the present invention 2 CO selectivity vs. study.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
The invention relates to a low-temperature plasma coupling bismuth-based MOF catalyst for reducing CO 2 Comprises the following steps:
1) Preparation of Bi-MOF catalyst:
dispersing 150mg of bismuth nitrate pentahydrate and 750mg of organic ligand in 60ml of organic solvent, magnetically stirring and mixing for at least 30min to obtain emulsion, placing the emulsion in a closed high-pressure reaction kettle, reacting for 24h at 100-120 ℃, obtaining a mixture with solid and liquid, filtering the solid in the mixture, washing for 3 times by the organic solvent, removing residues on the surface of the solid, and placing the washed solid in an oven at 60-80 ℃ for drying for 1-5h to obtain the metal organic framework compound-Bi-MOF catalyst.
The organic ligand in the invention adopts one of trimesic acid or terephthalic acid, or adopts trimesic acid and terephthalic acid at the same time;
the organic solvent is methanol or anhydrous methanol.
2) Reduction of CO 2 ：
Filling the Bi-MOF catalyst prepared in the step 1) and quartz sand into a discharge area of a low-temperature plasma reactor, and then introducing a gas-phase oxidant into the reactor at a gas inlet of the low-temperature plasma reactor, wherein the gas-phase oxidant is CO 2 . And then, adjusting the discharge condition of dielectric barrier discharge of the low-temperature plasma reactor to start discharge, so that the gas-phase oxidant is subjected to catalytic reaction on the surface of the Bi-MOF and quartz sand to generate CO, and the CO and other tail gases are discharged out of the reactor through a gas outlet of the low-temperature plasma reactor.
The low-temperature plasma reactor is a coaxial cylindrical DBD reactor, the coaxial cylindrical DBD reactor uses a stainless steel rod inserted into an inner tube to serve as a high-voltage electrode, a quartz tube reactor is used as a medium tube, and the outer electrode is a copper sheet and is used as a grounding electrode. The effective discharge area of the reactor is 50mm, the unilateral discharge gap is 3mm, and the discharge power range is 20-60w.
Comparative example 1
The reaction conditions are as follows: introducing 95vt% -100vt% of gas-phase oxidant CO into the low-temperature plasma reactor 2 The total flow was 30ml/min and the temperature in the catalytic chamber was 26 ℃.
The experimental steps are as follows: neither filling Bi-MOF catalyst in low temperature plasma reactorNor is it filled with quartz sand (i.e. empty tubes). CO is processed by 2 The gas is introduced into the dielectric barrier discharge reactor shown in fig. 1 from a gas inlet, catalytic reaction is carried out in a discharge area of the reactor to prepare CO, and CO and other tail gases are discharged through a gas outlet.
Conclusion: under the condition of plasma reaction, CO is realized 2 The conversion reaction to CO, as shown in FIG. 2, under the optimal condition, the CO selectivity reaches 78.93%, the CO yield reaches 7.58%, the conversion rate reaches 9.60%, and the energy efficiency is 1.35%.
Comparative example 2:
the reaction conditions are as follows: introducing 95vt% -100vt% of gas-phase oxidant CO into the low-temperature plasma reactor 2 The total flow was 30ml/min and the temperature in the catalytic chamber was 26 ℃.
The experimental steps are as follows: firstly, quartz sand is filled in a reactor, and CO 2 Introducing the gas into the dielectric barrier discharge reactor shown in fig. 1 from a gas inlet, carrying out catalytic reaction on the surface of quartz sand in a discharge area of the reactor to prepare CO, and discharging other tail gases through a gas outlet.
Conclusion: under the action of single quartz sand and the reaction conditions, the target product CO is generated by the reaction, as shown in figure 3, under the optimal conditions, the CO selectivity reaches 81.48%, the CO yield reaches 12.63%, the conversion rate reaches 15.50%, and the energy efficiency is 2.17%.
Example 1:
the difference from comparative example 2 is: 200mg and 3800mg of quartz sand were mixed and filled in the discharge region of the low-temperature plasma reactor.
The experimental steps are as follows: firstly, filling solid particles obtained by mixing 200mg of Bi-MOF catalyst and 3800mg of quartz sand into a low-temperature plasma reactor, and adding CO 2 Introducing the gas into the dielectric barrier discharge reactor shown in fig. 1 from a gas inlet, carrying out catalytic reaction on the surface of quartz sand in a discharge area of the reactor to prepare CO, and discharging other tail gases through a gas outlet.
Conclusion: after filling the Bi-MOF catalyst in the low temperature plasma reactor, as shown in fig. 6, the CO selectivity reaches 68.85%, the CO yield reaches 11.87%, the conversion reaches 17.23%, and the energy efficiency is 2.49% under the optimal conditions.
As shown in FIGS. 7 to 9, example 1 was compared with comparative examples 1 and 2, and CO was produced under the optimal conditions 2 Both conversion and energy efficiency are improved, and the CO yield is higher than in comparative example 1 and slightly lower than in comparative example 2.
Example 2:
the differences from example 1 are: the amount of Bi-MOF catalyst added was reduced, and the reaction conditions and experimental procedure were the same as those in example 1, reducing the amount of Bi-MOF catalyst in the discharge region to 100mg, and the total amount of Bi-MOF catalyst mixed with quartz sand was unchanged, i.e., 4g.
The experimental result of example 2 is shown in fig. 5, in which the CO selectivity and the energy efficiency are reduced with increasing discharge power, but the amplitude is extremely small; CO 2 Conversion rate and CO yield are increased; under the optimal conditions, CO 2 The conversion was 18.53%, the selectivity to CO was 69.97%, the CO yield was 12.97%, and the energy efficiency was 2.68%.
Conclusion: example 2 shows the CO yield and CO yield under the optimal conditions as shown in FIGS. 7 to 9, compared with comparative example 1 and comparative example 2 2 Both conversion and energy efficiency are improved. Example 2 As compared with example 1, as shown in FIGS. 7 to 9, the CO yield and CO of example 2 increased with the increase of the discharge power 2 Both conversion and energy efficiency were higher than in example 1.
Example 3:
the differences from examples 1 and 2 are: the amount of Bi-MOF catalyst added is further reduced; CO 2 The gas is different in total gas volume.
The reaction conditions and experimental procedure were the same as those in examples 1 and 2, and the amount of the Bi-MOF catalyst in the discharge region was reduced to 50mg, and the total amount of the Bi-MOF catalyst mixed with the quartz sand was unchanged, namely, 4g.
The experimental results of example 3 are shown in fig. 4, in which the energy efficiency tends to decrease as the power increases; CO 2 The conversion rate and the CO yield are increased, and the energy efficiency is greatly reduced when the discharge power is 20 w; under the optimal conditions, CO 2 The conversion was 20.04%, the selectivity to CO was 73.38%, the CO yield was 14.71%, and the energy efficiency was 3.44%.
Conclusion: example 3 shows the CO yield and CO yield under the optimal conditions as compared with comparative examples 1 and 2, as shown in FIGS. 7 to 9 2 Both conversion and energy efficiency are improved. Example 3 As compared with example 1 and example 2, as shown in FIGS. 7 to 9, the CO yield and CO yield of example 3 increased with the increase of the discharge power 2 Both conversion and energy efficiency were higher than in example 1 and example 2.
Table 1 shows the low temperature plasma reduction of CO under optimal conditions in accordance with the present invention 2 Is a table diagram of the performance of the (c).
| CO2 conversion | CO selectivity | CO yield | Energy efficiency | |
| Comparative example 1 | 9.60 | 78.93 | 7.58 | 1.35 |
| Comparative example 2 | 15.50 | 81.48 | 12.63 | 2.17 |
| Example 1 | 17.23 | 68.85 | 11.87 | 2.49 |
| Example 2 | 18.53 | 69.97 | 12.97 | 2.68 |
| Example 3 | 20.04 | 73.38 | 14.71 | 3.44 |
TABLE 1
The foregoing is merely a preferred embodiment of the invention, and it should be noted that modifications could be made by those skilled in the art without departing from the principles of the invention, which modifications would also be considered to be within the scope of the invention.
Claims (7)
1. CO reduction by low-temperature plasma coupling bismuth-based MOF catalyst 2 Is characterized in that: the method comprises the following steps:
1) Preparation of Bi-MOF catalyst:
dispersing 150mg of bismuth nitrate pentahydrate and 750mg of organic ligand in 60ml of organic solvent, magnetically stirring and mixing to obtain emulsion, placing the emulsion in a closed high-pressure reaction kettle for reaction to obtain a mixture with solid and liquid, filtering the solid in the mixture, washing the mixture for multiple times by the organic solvent to remove residues on the surface of the solid, and placing the washed solid in an oven for drying to obtain a metal organic framework compound-Bi-MOF catalyst;
2) Reduction of CO 2 ：
Filling the Bi-MOF catalyst prepared in the step 1) and quartz sand into a discharge area of a low-temperature plasma reactor, and then introducing a gas-phase oxidant into the reactor at a gas inlet of the low-temperature plasma reactor; and then, adjusting the discharge condition of dielectric barrier discharge of the low-temperature plasma reactor to start discharge, so that the gas-phase oxidant is subjected to catalytic reaction on the surface of the Bi-MOF and quartz sand to generate CO, and the CO and other tail gases are discharged out of the reactor through a gas outlet of the low-temperature plasma reactor.
2. The low temperature plasma coupled bismuth-based MOF catalyst for CO reduction as claimed in claim 1 2 Is characterized in that: in step 1):
the organic ligand adopts one of trimesic acid or terephthalic acid, or adopts trimesic acid and terephthalic acid at the same time;
the organic solvent is methanol or anhydrous methanol.
3. The low temperature plasma coupled bismuth-based MOF catalyst for CO reduction as claimed in claim 1 2 Is characterized in that: the gas phase oxidant is CO 2 ，CO 2 95vt% -100vt% of the total gas volume in the low temperature plasma reactor; CO 2 The total flow rate of (2) was 30ml/min.
4. A low temperature plasma coupled bismuth-based MOF catalyst as claimed in claim 3 for reduction of CO 2 Is characterized in that: the space velocity of the medium barrier discharge reaction zone in the low-temperature plasma reactor of the gas-phase oxidant is 50000-100000h -1 。
5. The low temperature plasma coupled bismuth-based MOF catalyst for CO reduction as claimed in claim 1 2 Is characterized in that:
in step 1): the magnetic stirring and mixing time is at least 30min;
placing the emulsion in a closed high-pressure reaction kettle, and reacting for 24 hours at 120 ℃ to obtain a mixture with solid and liquid;
the solid after standing and filtering is dried in an oven at 60-80 ℃ for 1-5h.
6. The low temperature plasma coupled bismuth-based MOF catalyst for CO reduction as claimed in claim 1 2 Is characterized in that: the total mass of the Bi-MOF catalyst and quartz sand filled in the discharge region of the low temperature plasma reactor was 4g.
7. The low temperature plasma coupled bismuth-based MOF catalyst for CO reduction as claimed in claim 1 2 Is characterized in that: the low-temperature plasma reactor is a coaxial cylindrical DBD reactor, the length of a discharge area of the low-temperature plasma reactor is 50mm, and the discharge power range is 20-60w.
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