CN114735648B - Oxygen carrier for chemical looping hydrogen production and preparation method and application thereof - Google Patents
Oxygen carrier for chemical looping hydrogen production and preparation method and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 105
- 239000001301 oxygen Substances 0.000 title claims abstract description 105
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000000126 substance Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013384 organic framework Substances 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 66
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 63
- 239000013207 UiO-66 Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 27
- 239000011572 manganese Substances 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- -1 inorganic acid salt Chemical class 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910007926 ZrCl Inorganic materials 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000013110 organic ligand Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000010926 purge Methods 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000004729 solvothermal method Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
- C01B3/063—Cyclic methods
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses an oxygen carrier for chemical environmental hydrogen production, a preparation method and application thereof. The method comprises the following steps: and introducing iron element and manganese element into the zirconium-containing organic framework material, and drying and roasting to obtain the oxygen carrier. The oxygen carrier prepared by the method has higher metal dispersity, better thermal stability and high-temperature reaction activity.
Description
Technical Field
The invention relates to an oxygen carrier for chemical looping hydrogen production and a preparation method and application thereof, in particular to an oxygen carrier for chemical looping hydrogen production with high activity and stability and a preparation method and application thereof.
Background
Chemical looping (Chemical looping) technology is a novel platform technology for Chemical conversion and energy utilization, which traps CO with low consumption 2 Advantages such as low NOx emission and exergy loss become one of the most promising technologies in the clean energy field.
The chemical ring hydrogen production technology replaces oxygen with lattice oxygen in the oxygen carrier, and under the high temperature condition, the oxygen carrier (MeO) and the fuel are subjected to oxidation-reduction reaction, so that the direct contact between the fuel and the air is avoided, the generation of NOx is reduced, and the cascade utilization of the fuel is realized through the cascade reduction of the oxygen carrier. The reduced oxygen carrier (Me) reacts with water vapor, and the product is simply condensed to obtain the hydrogen with higher purity. The reduction and oxidation reactions are alternately and circularly carried out in the reactor, so that continuous clean hydrogen production can be realized.
In recent years, about 900 oxygen carriers have been tested, and from the viewpoint of composition types, the oxygen carriers are mainly classified into two main types, namely, metal and nonmetal, wherein metal oxides are mainly used.
The stability and reactivity of the single-active component oxygen carrier are poor. Chinese patent CN110055120A adopts mechanical mixing method to make iron-base-Fe 2 O 3 The composite oxygen carrier is prepared by mixing copper-based-CuO and an inert oxygen carrier, and has the advantages of simple operation, low cost, poor sample uniformity and easy sintering in the reaction process. Tseng et al (Tseng Y.H., J.L.Ma, C.P.Chin, et al journalnal of the Taiwan Institute of Chemical Engineers, 2014, 45 (1): 174-179.) the composite nickel iron oxide was prepared by sol-gel method, and studies showed that the oxygen carrier had good redox activity, but sintering phenomenon occurred during the cycle as well due to metal aggregation.
In addition, inert carriers, such as Al, are added into the metal oxide oxygen carrier 2 O 3 、TiO 2 、SiO 2 And the like can also effectively improve the thermal stability of the oxygen carrier. Chinese patent CN111088090A, CN107539948B uses Fe respectively 2 O 3 And MoO 3 、Fe 2 O 3 And MgO is an active metal and is mixed and impregnated on an alumina carrier, and the obtained oxygen carrier has good thermal stability. However, the oxygen carrier prepared by the method has low load and is easy to be unevenly distributed. In addition Bhavsar (Bhavsar S., M. Najera, G. Veser. Chemical Engineering)&Technology, 2012, 35 (7): 1281-1290) and the like in Fe 2 O 3 Synthesis of Fe with core-shell Structure as active Metal 2 O 3 @SiO 2 An oxygen carrier. But the inert carrier readily forms FeAl with the active metal 2 O 4 、Fe 2 SiO 4 Inactive substances such as oxygen carrier reaction performance is reduced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides an oxygen carrier for chemical looping hydrogen production and a preparation method and application thereof. The oxygen carrier is simple to synthesize, and has higher metal dispersity, better thermal stability and high-temperature reaction activity.
An oxygen carrier production process for chemical looping hydrogen production, the process comprising: and introducing iron element and manganese element into the zirconium-containing organic framework material, and drying and roasting to obtain the oxygen carrier.
In the method, the zirconium-containing organic framework material is UiO-66, and the physical and chemical properties of the UiO-66 are as follows: particle diameter of 50-1000nm, specific surface area of 200-2000 m 2 And/g. The UiO-66 material can be commercially available or prepared according to the prior art, preferably using the prior art.
The preparation method of the UiO-66 adopts a solvothermal method for synthesis: a certain amount of ZrCl 4 Mixing and dissolving with an organic solvent Dimethylformamide (DMF); adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and placing the mixed solution into an incubator at a certain temperature for reaction for a period of time; and taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging and drying to obtain the UiO-66 material.
In the synthesis of the metal organic framework material by the solvothermal method, the reaction temperature is 80-200 ℃, preferably 100-180 ℃, the reaction time is 4-72 hours, preferably 12-24 hours, and the rotating speed is 100-400r/min.
In the above method, the Fe element is derived from at least one of an oxide, hydroxide, inorganic acid salt, organic acid salt, and chloride of Fe, and also includes hydrates of these compounds, among which water-soluble inorganic acid salt and chloride of Fe are preferable, and nitrate and chloride of Fe are more preferable.
In the above method, at least one of oxides, hydroxides, inorganic acid salts, and organic acid salts of Mn derived from Mn also includes hydrates of these compounds, and among them, water-soluble inorganic acid salts of Mn are preferable, and nitrate of Mn is more preferable.
In the method, the iron element and the manganese element are sequentially or simultaneously introduced to the zirconium-containing organic framework material, and the oxygen carrier is prepared after drying and roasting.
In the method, iron element and manganese element are introduced onto the zirconium-containing organic framework material in a dipping mode, and the oxygen carrier is prepared after drying and roasting.
In the method, the mass ratio of the introduced Fe element to the introduced Mn element in terms of oxide is (1-9) to 1, preferably (3-7) to 1.
In the above method, the Fe source and the Mn source are provided in the form of a solution, and co-impregnated and introduced onto the zirconium-containing organic framework material.
In the method, iron element and manganese element are introduced to the zirconium-containing organic framework material, citric acid is added for complexing, and the oxygen carrier is prepared after drying and roasting.
In the method, the molar ratio of the citric acid contained in the citric acid solution to the introduced metal element is (1-4): 1, preferably (1.5-2.5): 1.
in the above method, a specific embodiment comprises the steps of leading the Fe source and the Mn source to be co-impregnated and introduced onto a zirconium-containing organic framework material, adding citric acid to react under the condition of rotary heating, wherein the reaction temperature is 60-200 ℃, preferably 100-150 ℃, the reaction time is 4-72 hours, preferably 12-24 hours, and drying and roasting the reacted materials to obtain the oxygen carrier for the chemical looping hydrogen.
In the above method, the drying may be performed in a manner known in the art, and examples thereof include a spray drying method, a vacuum drying method, a thermal oven drying method, and the like. As the conditions for the drying, for example, a drying temperature of 60 to 150 ℃, preferably 100 to 120 ℃, and a drying time of 4 to 48 hours, preferably 6 to 36 hours, more preferably 8 to 24 hours can be mentioned.
In the method, the dried material is completely converted into the chemical looping hydrogen-producing oxygen carrier through the roasting. As the conditions for the calcination, for example, a calcination temperature of 400 to 1300 ℃, preferably 600 to 1200 ℃, more preferably 700 to 1000 ℃, and a calcination time of 3 to 10 hours, preferably 4 to 8 hours can be cited. The calcination may be performed in an oxygen-containing atmosphere (such as air) as needed.
The oxygen carrier for chemical environmental hydrogen production prepared by the method comprises the following steps of taking the weight of the oxygen carrier as a reference, wherein the weight content of ferric oxide in the oxygen carrier is 5% -65%, preferably 10% -60%, more preferably 20% -50%, and the manganese oxide content is 3% -30%, preferably 5% -20%, more preferably 8% -15%.
The application of the oxygen carrier adopts a fixed bed reactor, takes methane, CO or synthetic gas as raw materials, and has the reaction temperature of 500-1200 ℃, the reaction pressure of 0.1-5 mpa and the airspeed of 500-10000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; switching N when feedstock conversion drops significantly 2 Purging; introducing steam to react with the reduced oxygen carrier, condensing the product gas to obtain H 2 The method comprises the steps of carrying out a first treatment on the surface of the Switching N 2 Purging; and (5) introducing air to fully oxidize the oxygen carrier, so as to complete one-time cyclic reaction.
By using the oxygen carrier, the flow rate of the raw material gas is 100-500 ml/min, and the reaction time is 0.2-2 h.
In the application of the oxygen carrier, the distilled water inflow is 0.1-1.0 ml/min, the distilled water is vaporized into water vapor through a vaporization chamber, and the reaction time is 0.2-2 h.
Compared with the prior art, the oxygen carrier provided by the invention has better thermal stability and high-temperature reactivity in the chemical looping hydrogen production reaction process. The beneficial effects are that: the invention adopts UiO-66 material as MOFs carrier, and introduces Fe and Mn through adsorption and citric acid complexation reaction. Through directional regulation and control of the UiO-66 metal organic framework material structure, the high dispersion of Fe and Mn active metals is realized, and the difficult problem that Fe is easy to migrate and sinter at high temperature is effectively overcome; the UiO-66 material has higher specific surface area and thermal stability, and has better stability in the high-temperature reaction process of chemical looping hydrogen production; in addition, the multivalent state change property of Mn is fully utilized, and the transfer rate of lattice oxygen on an oxygen carrier is obviously improved, so that the reaction efficiency is improved.
Detailed Description
The preparation method of the oxygen carrier for chemical looping hydrogen production comprises the steps of adsorbing a UiO-66 material, complexing citric acid with a Fe source and a Mn source, and drying and roasting the material to obtain the oxygen carrier for chemical looping hydrogen production.
The UiO-66 material is synthesized by a solvothermal method in the method: a certain amount of ZrCl 4 Mixing and dissolving with an organic solvent Dimethylformamide (DMF); adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and placing the mixed solution into an incubator at a certain temperature for reaction for a period of time; and taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging and drying to obtain the UiO-66 material.
In the synthesis of the metal organic framework material by the solvothermal method, the reaction temperature is 80-200 ℃, preferably 100-180 ℃, and the reaction time is 4-72 hours, preferably 12-24 hours.
The citric acid complexation method comprises the following steps: first, a certain proportion of Fe (NO 3 ) 3 And Mn (NO) 3 ) 2 Dissolved in the water solution and fully adsorbed by the UiO-66 material. The adsorbed UiO-66 material was added to a citric acid solution, and heated and evaporated to dryness in a rotary evaporator, thereby obtaining a sol-gel substance. The oxygen carrier for chemical looping hydrogen production can be obtained through drying and roasting.
In the above-mentioned citric acid complexation method, the reaction temperature is 60-200 ℃, preferably 100-150 ℃, and the reaction time is 4-72 hours, preferably 12-24 hours.
In the above method, the roasting condition is that the roasting temperature is 400-1300 ℃, preferably 600-1200 ℃, more preferably 700-1000 ℃ under the air atmosphere; the calcination time is 1h to 24h, preferably 4h to 8h.
In the method of the invention, the calculation formula of the methane conversion rate is as follows:the method comprises the steps of carrying out a first treatment on the surface of the The calculation formula of the hydrogen yield comprises the following formula: />Wherein F N2 Is carrier gas N 2 Flow of S N2 Is carrier gas N 2 Peak area of S H2 Is H 2 Peak area, m OC Is the mass of the oxygen carrier.
Example 1
Weighing a certain amount of ZrCl 4 Adding into an organic solvent Dimethylformamide (DMF) for mixing and dissolving; dropwise adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 24 hours in a constant temperature box at 100 ℃; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 1600m 2 And/g. An amount of Fe (NO) 3 ) 3 And Mn (NO) 3 ) 2 Respectively dissolving in water solution, mixing and stirring uniformly; adding 5g of UiO-66 material into the mixed solution for full adsorption; adding the adsorbed UiO-66 material into citric acid solution, placing into a rotary evaporator, stirring at 120 ℃ at 130r/min, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain the oxygen carrier. The oxygen carrier is based on mass, wherein oxygenIron oxide content 43.2%, manganese oxide 11.73%, and the balance UIO-66.
The chemical looping hydrogen production reaction is carried out on a fixed bed reactor, methane is taken as a raw material, the reaction temperature is 800 ℃, the reaction pressure is 0.1Mpa, and the airspeed is 3000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; switching N when feedstock conversion drops significantly 2 Purging; introducing water vapor 0.1ml/min to perform steam reaction with the reduced oxygen carrier, condensing the product gas to obtain H 2 Analysis by gas chromatography; switching N 2 Purging; and (5) introducing air to fully oxidize the oxygen carrier. The methane conversion rate reaches 99.8%, and the single hydrogen production rate is 65ml/g.
Example 2
Weighing a certain amount of ZrCl 4 Adding into an organic solvent Dimethylformamide (DMF) for mixing and dissolving; dropwise adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 24 hours in a constant temperature box at 120 ℃; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 1450m 2 And/g. A certain amount of FeCl 3 And Mn (NO) 3 ) 2 Respectively dissolving in water solution, mixing and stirring uniformly; adding 5g of UiO-66 material into the mixed solution for full adsorption; adding the adsorbed UiO-66 material into citric acid solution, placing into a rotary evaporator, stirring at 120 ℃ at 80r/min, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain the oxygen carrier. The oxygen carrier is based on mass, wherein the content of ferric oxide is 57.1%, the content of manganese oxide is 14.2%, and the balance is UIO-66.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, synthesis gas is taken as raw material, the reaction temperature is 500 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 4000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; switching N when feedstock conversion drops significantly 2 Purging; introducing water vapor 0.4ml/min to perform steam reaction with the reduced oxygen carrier, condensing the product gas to obtain H 2 Analysis by gas chromatography; switching N 2 Purging; and (5) introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.9%, single timeThe hydrogen yield was 90ml/g.
Example 3
Weighing a certain amount of ZrCl 4 Adding into an organic solvent Dimethylformamide (DMF) for mixing and dissolving; dropwise adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 24 hours in a constant temperature box at 120 ℃; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 1450m 2 And/g. An amount of Fe (NO) 3 ) 3 And MnCl 2 Respectively dissolving in water solution, mixing and stirring uniformly; adding 5g of UiO-66 material into the mixed solution for full adsorption; adding the adsorbed UiO-66 material into citric acid solution, placing into a rotary evaporator, stirring at 120 ℃ at 90r/min, drying at 120 ℃, and roasting at 800 ℃ for 4 hours to obtain the oxygen carrier. The oxygen carrier is based on mass, wherein the content of ferric oxide is 37.5%, the content of manganese oxide is 6.3%, and the balance is UIO-66.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, synthesis gas is taken as raw material, the reaction temperature is 800 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 4000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; switching N when feedstock conversion drops significantly 2 Purging; introducing steam to react with the reduced oxygen carrier, condensing the product gas to obtain H 2 Analysis by gas chromatography; switching N 2 Purging; and (5) introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.9%, and the single hydrogen production amount is 100ml/g.
Example 4
Weighing a certain amount of ZrCl 4 Adding into an organic solvent Dimethylformamide (DMF) for mixing and dissolving; dropwise adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 30 hours in a 160 ℃ incubator; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 800m 2 And/g. A certain amount of FeCl is added according to the Fe/Mn molar ratio of 4 3 And Mn (NO) 3 ) 2 Respectively dissolving in water solution, mixing and stirring uniformly; taking 5g of UiO-66 material is added into the mixed solution for full adsorption; adding the adsorbed UiO-66 material into citric acid solution, placing into a rotary evaporator, stirring at 120 ℃ at 230r/min, drying at 100 ℃, and roasting at 550 ℃ for 4 hours to obtain the oxygen carrier. The oxygen carrier is based on the mass, wherein the content of ferric oxide is 48.8%, the content of manganese oxide is 13.3%, and the balance is UIO-66.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, synthesis gas is taken as raw material, the reaction temperature is 550 ℃, the reaction pressure is 0.3Mpa, and the airspeed is 6000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; switching N when feedstock conversion drops significantly 2 Purging; introducing water vapor 0.2ml/min to perform steam reaction with the reduced oxygen carrier, condensing the product gas to obtain H 2 Analysis by gas chromatography; switching N 2 Purging; and (5) introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.8%, and the single hydrogen production rate is 70ml/g.
Example 5
Weighing a certain amount of ZrCl 4 Adding into an organic solvent Dimethylformamide (DMF) for mixing and dissolving; dropwise adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 28 hours in a constant temperature box at 100 ℃; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 1280m 2 And/g. An amount of Fe (NO) 3 ) 3 And Mn (NO) 3 ) 2 Respectively dissolving in water solution, mixing and stirring uniformly; adding 5g of UiO-66 material into the mixed solution for full adsorption; adding the adsorbed UiO-66 material into citric acid solution, placing into a rotary evaporator, stirring at 120r/min, drying at 100 ℃ and roasting at 600 ℃ for 4 hours to obtain the oxygen carrier, wherein the oxygen carrier takes the mass as the standard, the iron oxide content is 38.9%, the manganese oxide content is 10.6%, and the balance is UIO-66.
The chemical looping hydrogen production reaction is carried out on a fixed bed reactor, CO is used as a raw material, the reaction temperature is 600 ℃, the reaction pressure is 0.1Mpa, and the airspeed is 2500h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; switching N when feedstock conversion drops significantly 2 Purging; introducing water vapor 0.1ml/min to perform steam reaction with the reduced oxygen carrier, condensing the product gas to obtain H 2 Analysis by gas chromatography; switching N 2 Purging; and (5) introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.9%, and the single hydrogen production amount is 85ml/g.
Example 6
Weighing a certain amount of ZrCl 4 Adding into an organic solvent Dimethylformamide (DMF) for mixing and dissolving; dropwise adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 22 hours in a constant temperature box at 110 ℃; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 1540m 2 And/g. An amount of Fe (NO) 3 ) 3 And Mn (NO) 3 ) 2 Respectively dissolving in water solution, mixing and stirring uniformly; adding 5g of UiO-66 material into the mixed solution for full adsorption; adding the adsorbed UiO-66 material into citric acid solution, placing into a rotary evaporator, stirring at 120 ℃ at 90r/min, drying at 110 ℃, and roasting at 550 ℃ for 6 hours to obtain the oxygen carrier. The oxygen carrier is based on the mass, wherein the iron oxide is 46.7%, the manganese oxide is 8.5%, and the rest is UIO-66.
The chemical looping hydrogen production reaction is carried out on a fixed bed reactor, CO is taken as a raw material, the reaction temperature is 550 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 4000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; switching N when feedstock conversion drops significantly 2 Purging; introducing water vapor 0.6ml/min to perform steam reaction with the reduced oxygen carrier, condensing the product gas to obtain H 2 Analysis by gas chromatography; switching N 2 Purging; and (5) introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.9%, and the single hydrogen production rate is 70ml/g.
Example 7
Weighing a certain amount of ZrCl 4 Adding into an organic solvent Dimethylformamide (DMF) for mixing and dissolving; dropwise adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 24 hours in a 130 ℃ incubator; the reactants are taken outRepeatedly washing with absolute ethanol, centrifuging, and drying to obtain UiO-66 material with specific surface area of 960m 2 And/g. A certain amount of FeCl 3 And MnCl 2 Respectively dissolving in water solution, mixing and stirring uniformly; adding 5g of UiO-66 material into the mixed solution for full adsorption; adding the adsorbed UiO-66 material into citric acid solution, placing into a rotary evaporator, stirring at 120 ℃ at 90r/min, drying at 110 ℃, and roasting at 650 ℃ for 6 hours to obtain the oxygen carrier. The oxygen carrier is based on mass, wherein the content of ferric oxide is 58.0%, the content of manganese oxide is 9.0%, and the balance is UIO-66.
The chemical looping hydrogen production reaction is carried out on a fixed bed reactor, CO is taken as a raw material, the reaction temperature is 650 ℃, the reaction pressure is 0.2Mpa, and the space velocity is 5000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; switching N when feedstock conversion drops significantly 2 Purging; introducing water vapor 0.3ml/min to perform steam reaction with the reduced oxygen carrier, condensing the product gas to obtain H 2 Analysis by gas chromatography; switching N 2 Purging; and (5) introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.8%, and the single hydrogen production amount is 80ml/g.
Example 8
Weighing a certain amount of ZrCl 4 Adding into an organic solvent Dimethylformamide (DMF) for mixing and dissolving; dropwise adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 25 hours in a constant temperature box at 120 ℃; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 1880m 2 And/g. An amount of Fe (NO) 3 ) 3 And Mn (NO) 3 ) 2 Respectively dissolving in water solution, mixing and stirring uniformly; adding 5g of UiO-66 material into the mixed solution for full adsorption; adding the adsorbed UiO-66 material into citric acid solution, placing into a rotary evaporator, stirring at 120 ℃ at 90r/min, drying at 110 ℃, and roasting at 650 ℃ for 6 hours to obtain the oxygen carrier. The oxygen carrier is based on the mass, wherein the content of ferric oxide is 40.8%, the content of manganese oxide is 8.1%, and the balance is UIO-66.
The chemical ring hydrogen production reaction is in a fixed bedThe reaction is carried out on a reactor, the synthesis gas is taken as a raw material, the reaction temperature is 650 ℃, the reaction pressure is 0.2Mpa, and the airspeed is 4500h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; switching N when feedstock conversion drops significantly 2 Purging; introducing water vapor 0.2ml/min to perform steam reaction with the reduced oxygen carrier, condensing the product gas to obtain H 2 Analysis by gas chromatography; switching N 2 Purging; and (5) introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.9%, and the single hydrogen production amount is 110ml/g.
Comparative example 1
The oxygen carrier was prepared as in example 6, except that UiO-66 was not used as a carrier, and only Fe-Mn composite metal oxygen carrier was obtained. Oxygen carrier evaluation conditions were the same as in example 6, and sampling analysis was performed during the reduction and hydrogen production processes. CO conversion was 75.6% and hydrogen production was 25ml/gcat.
Comparative example 2
The oxygen carrier was prepared as in example 6, except that no metal Mn was added. Oxygen carrier evaluation conditions were the same as in example 6, and sampling analysis was performed during the reduction and hydrogen production processes. The CO conversion was 86.5% and the hydrogen yield was 32ml/gcat.
Claims (7)
1. An oxygen carrier preparation method for chemical looping hydrogen production, which is characterized by comprising the following steps: the method comprises the following steps: introducing iron element and manganese element into a zirconium-containing organic framework material, adding citric acid for complexing, and drying and roasting to obtain an oxygen carrier, wherein the mass ratio of the introduced Fe element and Mn element calculated as oxides is (3-7) to 1, the drying temperature is 60-150 ℃, the drying time is 4-48 hours, the roasting temperature is 400-1300 ℃, and the roasting time is 3-10 hours, wherein the iron element and manganese element are introduced by providing Fe source and Mn source in the form of solution, and are co-impregnated and introduced into the zirconium-containing organic framework material, the Fe element is at least one of oxide, hydroxide, inorganic acid salt, organic acid salt and chloride of Fe, the Mn element is at least one of oxide, hydroxide, inorganic acid salt and organic acid salt of Mn, the zirconium-containing organic framework material is UiO-66, and the physicochemical properties of the UiO-66 are as follows: particle size50-1000nm, and specific surface area of 800-2000m 2 And/g, the synthesis method of the UiO-66 comprises the following steps: a certain amount of ZrCl 4 Mixing and dissolving with an organic solvent Dimethylformamide (DMF); adding organic ligand terephthalic acid, continuously stirring and dissolving, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and placing the mixed solution into an incubator at a certain temperature for reaction for a period of time; and taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging and drying to obtain the UiO-66 material.
2. The method according to claim 1, characterized in that: the reaction temperature is 80-200 ℃ and the reaction time is 4-72 hours, and the rotating speed is 100-400r/min.
3. The method according to claim 1, characterized in that: the molar ratio of citric acid contained in the citric acid solution to the introduced metal element is (1-4): 1.
4. the method according to claim 1, characterized in that: adding citric acid to react under the condition of rotary heating, wherein the reaction temperature is 60-200 ℃, the reaction time is 4-72 hours, and the oxygen carrier for preparing the hydrogen by chemical looping is obtained by drying and roasting the reacted materials.
5. An oxygen carrier for chemical looping hydrogen produced by the method of any one of claims 1 to 4, characterized in that: based on the weight of the oxygen carrier, the weight content of the ferric oxide in the oxygen carrier is 5-65%, and the manganese oxide content is 3-30%.
6. Use of an oxygen carrier for chemical looping hydrogen as claimed in claim 5, wherein: adopting a fixed bed reactor, taking methane, CO or synthetic gas as raw material gas, wherein the reaction temperature is 500-1200 ℃, the reaction pressure is 0.1-5 mpa, and the space velocity is 500-10000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reacting with oxygen carrier in reactor to generate reduction reaction; after the reduction reaction is finished, steam and the reduced oxygen carrier are introduced to perform oxidation reaction, and the oxidation-reduction reaction is circularly performed.
7. The use according to claim 6, characterized in that: the flow rate of the raw material gas is 100-500 ml/min, and the reaction time is 0.2-2 h.
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Effective date of registration: 20231225 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |