CN114735645B - Oxygen carrier and preparation method and application thereof - Google Patents
Oxygen carrier and preparation method and application thereof Download PDFInfo
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- CN114735645B CN114735645B CN202110018634.XA CN202110018634A CN114735645B CN 114735645 B CN114735645 B CN 114735645B CN 202110018634 A CN202110018634 A CN 202110018634A CN 114735645 B CN114735645 B CN 114735645B
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 110
- 239000001301 oxygen Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 239000000463 material Substances 0.000 claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 26
- 239000013384 organic framework Substances 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 78
- 239000013207 UiO-66 Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 52
- 238000001035 drying Methods 0.000 claims description 36
- 239000010949 copper Substances 0.000 claims description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 25
- -1 polytetrafluoroethylene Polymers 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000013110 organic ligand Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910007926 ZrCl Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 30
- 239000001257 hydrogen Substances 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 20
- 238000010926 purge Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 229960004643 cupric oxide Drugs 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000009736 wetting Methods 0.000 description 8
- 239000005751 Copper oxide Substances 0.000 description 6
- 229910000431 copper oxide Inorganic materials 0.000 description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 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
- 238000004364 calculation method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910002549 Fe–Cu Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000003860 storage 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
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- 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
Abstract
The invention discloses an oxygen carrier, a preparation method and application thereof. The oxygen carrier takes a zirconium-containing organic framework material as a carrier and Fe as an active component, wherein the weight content of zirconium in the zirconium-containing organic framework material is 30-85%, preferably 35-75%, and more preferably 40-70% in terms of oxide; zirconium and iron in the oxygen carrier are respectively calculated by zirconium oxide and iron oxide, and the weight ratio of the zirconium oxide to the iron oxide is (1-8): 1, preferably (2-5): 1. the oxygen carrier has the advantages of simple synthesis, high dispersity of active components, good high-temperature reaction activity and the like.
Description
Technical Field
The invention relates to an oxygen carrier and a preparation method and application thereof, in particular to an oxygen carrier with high activity and stability and a preparation method and application thereof.
Background
The chemical looping technique is a novel chemical conversion and energy utilization technique that utilizes chemical intermediates to decompose a desired reaction into a plurality of sub-reactions, and utilizes lattice oxygen in an oxygen carrier instead of pure oxygen to prevent fuel from contacting air. The chemical looping concept was originally proposed in a hydrogen-producing patent by Lane in 1913, and was first applied to chemical looping combustion in 1983. Chemical looping hydrogen production technology for capturing CO with low consumption 2 Advantages such as low NOx emission, high conversion rate and energy utilization rate, etc., become one of the most promising technologies in the clean energy field.
Oxygen carrier materials in chemical looping reactions play a more important role in achieving high efficiency than traditional fuel conversion processes. It is generally considered that Fe is produced by integrating the factors such as oxygen carrier price, oxygen carrying capacity, raw material conversion rate, steam conversion rate, mechanical strength and the like 2 O 3 Is more suitable for the chemical looping hydrogen production process. Pure Fe 2 O 3 The oxygen carrier is very easy to sinter, and the specific surface area and the porosity are reduced.
Bohn et al (Bohn C D, cleeton J P. Energy)&Fuels,2010, 24 (7): 4025-4033.) various inert carriers (Al) were prepared by spray drying 2 O 3 、SiO 2 MgO) is contained in the oxygen carrier,at CO or H 2 Can keep stronger stability in the process of preparing hydrogen by chemical looping for raw materials. 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 obtained by the method has low load and FeAl is easy to form in the circulating process 2 O 4 ，Fe 2 SiO 4 And inert iron oxide, and reduces oxygen storage capacity and reactivity of the oxygen carrier.
The existing commonly used load-type oxygen carrier has the problems of low porosity, uneven dispersion of active components, reduced reactivity due to the interaction of the active components and inert carriers, and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides an oxygen carrier, and a preparation method and application thereof. The oxygen carrier is simple to synthesize, and has higher dispersity, better high-temperature reaction activity and higher raw material conversion rate.
An oxygen carrier, which takes a zirconium-containing organic framework material as a carrier and Fe as an active component, wherein the weight content of zirconium in the zirconium-containing organic framework material is 30-85%, preferably 35-75%, and more preferably 40-70% in terms of oxide; zirconium and iron in the oxygen carrier are respectively calculated by zirconium oxide and iron oxide, and the weight ratio of the zirconium oxide to the iron oxide is (1-8): 1, preferably (2-5): 1.
the oxygen carrier may further contain Cu element, and the mass ratio of Fe element to Cu element in the oxygen carrier is (1-9) to 1, preferably (3-7) to 1, in terms of oxide.
In the oxygen carrier, the zirconium organic framework material is UiO-66, and the UiO-66 can be purchased commercially or prepared according to the prior art. The physical and chemical properties of the UiO-66 material are as follows: the particle size is 500-5000nm, and the specific surface area is 200-2000 m2/g.
A non-limiting method for preparing UIO-66 comprises the following steps: mixing a certain amount of ZrCl4 with an organic solvent Dimethylformamide (DMF) for dissolution; 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; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging and drying to obtain a UiO-66 material; 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.
A method of preparing an oxygen carrier, the method comprising: and (3) taking the zirconium organic framework material as a carrier, introducing iron element into the zirconium organic framework material by contacting an iron source with the zirconium organic framework material, and drying to obtain the final oxygen carrier for preparing hydrogen by chemical chains.
In the method, the zirconium organic framework material is UiO-66, and the UiO-66 can be purchased commercially or prepared according to the prior art. The physical and chemical properties of the UiO-66 material are as follows: particle diameter of 500-5000nm, specific surface area of 200-2000 m 2 /g。
A non-limiting method for preparing 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; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging and drying to obtain a UiO-66 material; 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 source includes at least one of an oxide, hydroxide, inorganic acid salt, organic acid salt, and chloride of Fe, and also includes hydrates of these compounds, wherein water-soluble inorganic acid salt and chloride of Fe are preferable, and nitrate and chloride of Fe are more preferable.
In the method, the copper source is contacted with the zirconium organic framework material to introduce the copper element before, simultaneously with or after the zirconium organic framework material is introduced with the iron element. The Cu source comprises at least one of an oxide, hydroxide, inorganic acid salt and organic acid salt of Cu, and also comprises hydrates of the compounds, wherein water-soluble inorganic acid salt of Cu is preferred, and nitrate of Cu is more preferred.
In the above method, the mass ratio of the Fe source and the Cu source in terms of Fe and Cu element oxides is (1-9) to 1, preferably (3-7) to 1.
In the above method, the Fe source and the Cu source are preferably supplied in the form of a solution to form a co-impregnation liquid.
In the above method, a specific embodiment includes adding the Fe source, the impregnation solution of the Cu source, and UiO-66 into a reaction system (such as a reaction vessel) sequentially or simultaneously according to a predetermined amount, and drying the materials to obtain the chemical looping hydrogen-producing oxygen carrier.
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 above method, the oxygen carrier may also be shaped into a suitable particle form, such as a bar shape, a sheet shape, a column shape, a sphere shape, a zigzag shape, or the like, according to the technique known in the art, as required. For example, the oxygen carrier of chemical looping hydrogen is mixed with a binder (preferably pseudo-boehmite) and then kneaded, molded and dried to obtain the required product.
In the application of the oxygen carrier, the roasted oxygen carrier is filled in a fixed bed reactor, synthesis gas is used as a raw material, the reaction temperature is 400-1000 ℃, the reaction pressure is 0.1-5 mpa, and the space velocity is 100-10000 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.
In the above application, the dried material is completely converted into a composite oxide by the firing. As the conditions for the calcination, for example, a calcination temperature of 300 to 1000 ℃, preferably 400 to 900 ℃, more preferably 600 to 800 ℃, 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.
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.
Detailed Description
An oxygen carrier for preparing hydrogen by chemical ring is prepared through immersing the soluble solution containing Fe and Cu in UiO-66 carrier, and drying.
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 ℃, the reaction time is 4-72 hours, preferably 12-24 hours, and the rotating speed is 100-400r/min.
Co-impregnation process in the above method: first, a certain proportion of Fe (NO 3 ) 3 And Cu (NO) 3 ) 2 Dissolved in the water solution and fully adsorbed by the UiO-66 material. And (3) rotationally heating and evaporating the material in a rotary evaporator, and drying, forming and roasting to obtain the chemical looping hydrogen and oxygen carrier.
In the above method, the baking condition is that the baking temperature is 300-1000 ℃, preferably 400-900 ℃, more preferably 600-800 ℃ and the baking time is 3-10 hours, preferably 4-8 hours under the air atmosphere. .
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 1450m 2 And/g. An amount of Fe (NO) 3 ) 3 And Cu (NO) 3 ) 2 Dissolving in water solution, mixing and stirring to form soaking solution; dripping the dipping liquid into 5g of UiO-66 material for full wetting; the adsorbed UiO-66 material is put into a rotary evaporator and is stirred and evaporated to dryness at the speed of 120r/min at the temperature of 50 ℃. And drying at 120 ℃ to obtain an oxygen carrier, wherein the oxygen carrier takes the mass as a standard, the content of ferric oxide is 46.2%, the content of copper oxide is 7.7%, and the content of UIO-66 is 46.1%.
Roasting the oxygen carrier at 600 ℃ for 4 hours, performing chemical looping hydrogen production reaction, and performing the reaction on a fixed bed reactor by taking synthesis gas as a raw material, wherein the reaction temperature is 600 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 800 hours -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 99.8%, and the single hydrogen production amount is 80ml/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 130 ℃ incubator; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 1150m 2 And/g. A certain amount of FeCl 3 And Cu (NO) 3 ) 2 Dissolving in water solution, mixing and stirring to form soaking solution; dripping the dipping liquid into the UiO-66 material for full wetting; the adsorbed UiO-66 material is put into a rotary evaporator and is stirred and evaporated to dryness at the speed of 120r/min at the temperature of 50 ℃. And drying at 120 ℃ to obtain an oxygen carrier, wherein the oxygen carrier takes the mass as a standard, the content of ferric oxide is 31.4%, the content of copper oxide is 5.8%, and the content of UIO-66 is 62.8%.
Roasting the oxygen carrier at 500 ℃ for 4 hours, then carrying out chemical looping hydrogen production reaction, wherein the reaction is carried out on a fixed bed reactor, synthesis gas is taken as a raw material, the reaction temperature is 500 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 800 hours -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 99.8%, and the single hydrogen production amount is 60ml/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 28 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 1600m 2 And/g. An amount of Fe (NO) 3 ) 3 And Cu (NO) 3 ) 2 Dissolving in water solution, mixing and stirring to form soaking solution; dripping the dipping liquid into the UiO-66 material for full wetting; the adsorbed UiO-66 material is put into a rotary evaporator and is stirred and evaporated to dryness at the speed of 90r/min at the temperature of 50 ℃. And drying at 120 ℃ to obtain the oxygen carrier. By oxygen carriersThe mass of (2) is standard, wherein the content of ferric oxide is 44.4%, the content of cupric oxide is 11.1%, and the content of UIO-66 is 44.4%.
Roasting the oxygen carrier at 550 ℃ for 4 hours, then carrying out chemical looping hydrogen production reaction, wherein the reaction is carried out on a fixed bed reactor, synthesis gas is taken as a raw material, the reaction temperature is 550 ℃, the reaction pressure is 0.1Mpa, and the airspeed is 1000 hours -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 90ml/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 22 hours in a constant temperature box at 140 ℃; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 1160m 2 And/g. A certain amount of FeCl is added according to the Fe/Cu molar ratio of 5 3 And Cu (NO) 3 ) 2 Dissolving in water solution, mixing and stirring to form soaking solution; dripping the dipping liquid into the UiO-66 material for full wetting; the adsorbed UiO-66 material is put into a rotary evaporator and is stirred and evaporated to dryness at the speed of 100r/min at the temperature of 60 ℃. And drying at 120 ℃ to obtain an oxygen carrier, wherein the oxygen carrier takes the mass as a standard, the iron oxide content is 29.0%, the copper oxide content is 7.2%, and the UIO-66 content is 63.8%.
Roasting the oxygen carrier at 550 ℃ for 5 hours, then carrying out chemical looping hydrogen production reaction, wherein the reaction is carried out on a fixed bed reactor, synthesis gas is taken as a raw material, the reaction temperature is 550 ℃, the reaction pressure is 0.1Mpa, and the airspeed is 3500 hours -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 99.8%, and the single hydrogen production amount is 95ml/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 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 1480m 2 And/g. An amount of Fe (NO) 3 ) 3 And Cu (NO) 3 ) 2 Dissolving in water solution, mixing and stirring to form soaking solution; dripping the dipping liquid into the UiO-66 material for full wetting; the adsorbed UiO-66 material is put into a rotary evaporator and is stirred and evaporated to dryness at the speed of 120r/min at the temperature of 50 ℃. And drying at 120 ℃ to obtain an oxygen carrier, wherein the oxygen carrier takes the mass as a standard, the iron oxide content is 41.6%, the copper oxide content is 8.4%, and the UIO-66 content is 50.0%.
Roasting the oxygen carrier at 600 ℃ for 4 hours, then carrying out chemical looping hydrogen production reaction, wherein the reaction is carried out on a fixed bed reactor, synthesis gas is taken as a raw material, the reaction temperature is 600 ℃, the reaction pressure is 0.1Mpa, and the airspeed is 3500 hours -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 90ml/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 18 hours in a 130 ℃ incubator; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 680m 2 And/g. Will be a certain amountFe(NO 3 ) 3 And CuCl 2 Dissolving in water solution, mixing and stirring to form soaking solution; dripping the dipping liquid into the UiO-66 material for full wetting; the adsorbed UiO-66 material is put into a rotary evaporator and is stirred and evaporated to dryness at the speed of 120r/min at the temperature of 50 ℃. And drying at 120 ℃ to obtain an oxygen carrier, wherein the oxygen carrier takes the mass as a standard, the content of ferric oxide is 37.0%, the content of copper oxide is 7.5%, and the content of UIO-66 is 55.5%.
Roasting the oxygen carrier at 480 ℃ for 4 hours, then carrying out chemical looping hydrogen production reaction, and carrying out the reaction on a fixed bed reactor, wherein synthesis gas is used as a raw material, the reaction temperature is 480 ℃, the reaction pressure is 0.3Mpa, and the space velocity is 4000 hours -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 65ml/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 26 hours in a 130 ℃ incubator; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging, drying to obtain UiO-66 material with specific surface area of 1060m 2 And/g. A certain amount of FeCl 3 And CuCl 2 Dissolving in water solution, mixing and stirring to form soaking solution; dripping the dipping liquid into the UiO-66 material for full wetting; the adsorbed UiO-66 material is put into a rotary evaporator and is stirred and evaporated to dryness at the speed of 90r/min at the temperature of 60 ℃. And drying at 110 ℃ to obtain the oxygen carrier. The oxygen carrier is based on mass, wherein the content of ferric oxide is 42.2%, the content of cupric oxide is 10.5%, and the content of UIO-66 is 47.3%.
Roasting the oxygen carrier at 500 ℃ for 4 hours, then carrying out chemical looping hydrogen production reaction, wherein the reaction is carried out on a fixed bed reactor, synthesis gas is taken as a raw material, the reaction temperature is 500 ℃, the reaction pressure is 0.2Mpa, and the space velocity is 2000 hours -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 99.8%, and the single hydrogen production amount is 65ml/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 20 hours in a constant temperature box at 120 ℃ with the specific surface area of 1460m 2 /g; and taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging and drying to obtain the UiO-66 material. An amount of Fe (NO) 3 ) 3 And Cu (NO) 3 ) 2 Dissolving in water solution, mixing and stirring to form soaking solution; dripping the dipping liquid into the UiO-66 material for full wetting; the adsorbed UiO-66 material is put into a rotary evaporator and is stirred and evaporated to dryness at the speed of 120r/min at the temperature of 50 ℃. And drying at 120 ℃ to obtain an oxygen carrier, wherein the oxygen carrier takes the mass as a standard, the iron oxide content is 27.4%, the copper oxide content is 3.9%, and the UIO-66 content is 68.6%.
Roasting the oxygen carrier at 600 ℃ for 4 hours, then carrying out chemical looping hydrogen production reaction, wherein the reaction is carried out on a fixed bed reactor, synthesis gas is taken as a raw material, the reaction temperature is 500 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 6000 hours -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 99.8%, and the single hydrogen production rate is 64ml/g.
Comparative example 1
The oxygen carrier was prepared as in example 5, except that UiO-66 was not used as a carrier, and only Fe-Cu composite metal oxygen carrier was obtained. Oxygen carrier evaluation conditions were the same as in example 5, and sampling analysis was performed during reduction and hydrogen production. The CO conversion was 70.6% and the hydrogen yield was 22ml/gcat.
Comparative example 2
The oxygen carrier was prepared as in example 5, except that no metallic Cu was added. Oxygen carrier evaluation conditions were the same as in example 5, and sampling analysis was performed during reduction and hydrogen production. The CO conversion was 80.8% and the hydrogen yield was 33ml/gcat.
Claims (20)
1. An oxygen carrier, characterized in that: the oxygen carrier takes a zirconium-containing organic framework material as a carrier and Fe as an active component, wherein the weight content of zirconium in the zirconium-containing organic framework material is 30-85% in terms of oxide; zirconium and iron in the oxygen carrier are respectively calculated by zirconium oxide and iron oxide, and the weight ratio of the zirconium oxide to the iron oxide is (1-8): 1, the oxygen carrier contains Cu element, the mass ratio of Fe and Cu elements in the oxygen carrier is (1-9) to 1 in terms of oxide, the zirconium organic framework material is UiO-66, and the physicochemical properties of the UiO-66 material are as follows: particle diameter of 500-5000nm, specific surface area of 200-2000 m 2 The preparation 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. An oxygen carrier according to claim 1, wherein: the mass ratio of Fe and Cu elements in the oxygen carrier is (3-7) to 1 in terms of oxide.
3. An oxygen carrier according to claim 1, wherein: the weight content of zirconium in the zirconium-containing organic framework material is 35-75% in terms of oxide; zirconium and iron in the oxygen carrier are respectively calculated by zirconium oxide and iron oxide, and the weight ratio of the zirconium oxide to the iron oxide is (2-5): 1.
4. a process for the preparation of an oxygen carrier according to any one of claims 1 to 3, characterized in that: the method comprises the following steps: and (3) taking a zirconium organic framework material as a carrier, introducing iron element into the organic framework material by contacting an iron source and a copper source with the zirconium organic framework material, and drying to obtain the final oxygen carrier.
5. The method according to claim 4, wherein: the zirconium organic framework material is UiO-66, and the physical and chemical properties of the UiO-66 material are as follows: particle diameter of 500-5000nm, specific surface area of 200-2000 m 2 /g。
6. The method according to claim 5, wherein: the preparation 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; taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging and drying to obtain a UiO-66 material; the reaction temperature is 80-200 ℃, the reaction time is 4-72 hours, and the rotating speed is 100-400r/min.
7. The method according to claim 6, wherein: the reaction temperature is 100-180 ℃ and the reaction time is 12-24 hours.
8. The method according to claim 4, wherein: the Fe source comprises at least one of an oxide, a hydroxide, an inorganic acid salt, an organic acid salt and a chloride of Fe, and the Cu source comprises at least one of an oxide, a hydroxide, an inorganic acid salt and an organic acid salt of Cu.
9. The method according to claim 4, wherein: the mass ratio of the Fe source to the Cu source is (1-9) to 1 in terms of Fe and Cu element oxides.
10. A method according to claim 3, characterized in that: the mass ratio of the Fe source to the Cu source is (3-7) to 1 in terms of Fe and Cu element oxides.
11. The method according to claim 4, wherein: the Fe source and the Cu source are provided in the form of a solution to form a co-impregnation liquid.
12. The method according to claim 4, wherein: the method comprises the steps of sequentially or simultaneously adding the Fe source, the Cu source impregnating solution and the UiO-66 into a reaction system according to a preset dosage, and drying the materials to obtain the oxygen carrier.
13. The method according to claim 4, wherein: the drying temperature is 60-150 ℃ and the drying time is 4-48 hours.
14. The method according to claim 13, wherein: the drying temperature is 100-120 ℃ and the drying time is 6-36 hours.
15. The method according to claim 13, wherein: drying time is 8-24 hours.
16. The use of an oxygen carrier according to any one of claims 1 to 3, wherein the oxygen carrier after calcination is filled in a fixed bed reactor or is filled in a fixed bed reactor and then calcined, and synthesis gas is used as raw material gas, the reaction temperature is 400 to 1000 ℃, the reaction pressure is 0.1 to 5MPa, and the space velocity is 100 to 10000h -1 。
17. The use according to claim 16, characterized in that: roasting temperature is 300-1000 ℃ and roasting time is 3-10 hours.
18. The use according to claim 17, characterized in that: roasting temperature is 400-900 ℃ and roasting time is 4-8 hours.
19. The use according to claim 18, characterized in that: the roasting temperature is 600-800 ℃.
20. The use according to claim 16, 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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