CN116459835A - Co-Fe-based photo-thermal oxygen carrier and preparation method and application thereof - Google Patents
Co-Fe-based photo-thermal oxygen carrier and preparation method and application thereof Download PDFInfo
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- CN116459835A CN116459835A CN202310462956.2A CN202310462956A CN116459835A CN 116459835 A CN116459835 A CN 116459835A CN 202310462956 A CN202310462956 A CN 202310462956A CN 116459835 A CN116459835 A CN 116459835A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000001301 oxygen Substances 0.000 title claims abstract description 78
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 78
- 229910020598 Co Fe Inorganic materials 0.000 title claims abstract description 60
- 229910002519 Co-Fe Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000002407 reforming Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000446 fuel Substances 0.000 claims description 47
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005286 illumination Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 238000003980 solgel method Methods 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
- 239000002028 Biomass Substances 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
- C01B3/363—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents characterised by the burner used
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- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
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- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1252—Cyclic or aromatic hydrocarbons
Abstract
The invention provides a Co-Fe-based photo-thermal oxygen carrier, and a preparation method and application thereof. The Co-Fe-based photo-thermal oxygen carrier is prepared by adopting a ball milling method, can be applied to a photo-thermal chemical chain reforming Co-preparation hydrogen and synthesis gas process, and realizes high-efficiency conversion of toluene and preparation of high-concentration hydrogen at 615 ℃ under a lower reaction temperature. Compared with the conventional technology, the temperature is at least 900 ℃ in order to achieve the same toluene conversion rate without using a light source.
Description
Technical Field
The invention belongs to the technical field of hydrogen preparation, and particularly relates to a Co-Fe-based photo-thermal oxygen carrier, and a preparation method and application thereof.
Background
The hydrogen energy is used as a clean and high-efficiency energy source with high energy density, plays an important role in solving the energy crisis, global warming, environmental pollution and the like, and has important significance for realizing the double-carbon target in China by developing the low-carbon hydrogen production technology. The chemical-looping hydrogen production technology is a novel zero-carbon-emission hydrogen production technology, and even the negative carbon emission in the hydrogen production process can be realized if biomass-based fuel is adopted as a raw material. However, the following technical problems are generally existed in the chemical-looping hydrogen production technology at the present stage: low lattice oxygen activity at low temperatures results in low fuel conversion; oxygen carriers are prone to sinter deactivation at high temperatures. Although the oxygen activity and stability are improved to a certain extent by doping modification, the problems of high energy consumption, large equipment investment and the like caused by higher reaction temperature still face to realize industrial application. Therefore, development of a novel chemical looping hydrogen production technology under mild conditions is needed.
In recent years, more and more researches are conducted to introduce solar energy into a thermal catalytic system (i.e. a photo-thermal catalytic technology), and it is hoped to solve the technical difficulties faced by the conventional thermal conversion technology. The prior photo-thermal catalysis technology strategy has initial effects in the traditional thermochemical fields such as methane reforming hydrogen production, fischer-Tropsch synthesis and the like. Compared with the traditional thermochemical technology, the construction of the photo-thermal catalytic system helps to improve the product selectivity, activate the intermediate product and reduce the total reaction energy barrier. In addition, the photo-thermal effect can also provide sufficient thermal energy for thermodynamically unfavorable reactions, so that severe reaction conditions (e.g., high temperature and high pressure) can be avoided to some extent. Chemical-looping hydrogen production belongs to the category of thermal conversion technology, and coupling photocatalysis is an effective means for solving the technical problem of chemical-looping hydrogen production.
Disclosure of Invention
In view of the above, the invention provides a Co-Fe-based photo-thermal oxygen carrier, and a preparation method and application thereof, so as to solve the technical problems in the prior art.
In a first aspect, the invention provides a preparation method of a Co-Fe-based photo-thermal oxygen carrier, which comprises the following steps:
mixing a Co source and a Fe source to obtain a mixture;
and ball milling the mixture, and calcining to obtain the Co-Fe-based photo-thermal oxygen carrier.
Preferably, the preparation method of the Co-Fe-based photo-thermal oxygen carrier has the calcination temperature of 900-1100 ℃ and the calcination time of 4-8 hours.
Preferably, in the preparation method of the Co-Fe-based photo-thermal oxygen carrier, in the step of ball milling the mixture, the ball milling rotating speed is 500-700 rpm, the ball milling time is 2-6 h, and the ball-material ratio is (4-6): 1.
Preferably, the molar ratio of the Co source to the Fe source is (1-3) (1-4).
Preferably, the preparation method of the Co-Fe-based photo-thermal oxygen carrier comprises the steps of CoO and Co 3 O 4 Any one of them;
the Fe comprises Fe 2 O 3 、Fe 3 O 4 Either FeO or Fe.
In a second aspect, the invention also provides a Co-Fe-based photo-thermal oxygen carrier, which is prepared by the preparation method.
In a third aspect, the invention also provides a Co-Fe-based photo-thermal oxygen carrier prepared by the preparation method or application of the Co-Fe-based photo-thermal oxygen carrier in a chemical chain reforming coupling hydrogen production and synthesis gas process.
Preferably, the application comprises: placing a Co-Fe-based photo-thermal oxygen carrier in a fuel reactor, starting a light source and an electric furnace to heat the fuel reactor, introducing fuel into the fuel reactor after reaching a target temperature, and reacting to obtain synthesis gas;
placing the Co-Fe-based photo-thermal oxygen carrier after the reaction of the fuel reactor in a steam reactor, starting a light source and an electric furnace to heat the fuel reactor, and introducing the Co-Fe-based photo-thermal oxygen carrier into the steam reactor after reaching a target temperatureThe water vapor is reacted to obtain H 2 。
Preferably, the fuel comprises toluene and/or steam for the application;
and (3) starting the light source and the electric furnace to heat the fuel reactor, wherein in the step of reaching the target temperature, the current of the light source is controlled to be 10-20A, and the target temperature is controlled to be 400-700 ℃.
Preferably, in the step of introducing fuel into the fuel reactor, the flow rate of the fuel is 0.01-0.1 mL/min;
and placing the Co-Fe-based photo-thermal oxygen carrier into a fuel reactor, wherein the mass of the Co-Fe-based photo-thermal oxygen carrier is 1-2 g.
Compared with the prior art, the Co-Fe-based photo-thermal oxygen carrier and the preparation method and application thereof have the following beneficial effects:
the Co-Fe-based photothermal oxygen carrier is prepared by adopting a ball milling method, and compared with the oxygen carrier prepared by the traditional sol-gel method, the photothermal chemical chain hydrogen production performance is particularly better; the Co-Fe-based photo-thermal oxygen carrier can be applied to the photo-thermal chemical chain technology for preparing hydrogen, and the temperature of the chemical chain hydrogen is reduced to 615 ℃, compared with the traditional technology, the Co-Fe-based photo-thermal oxygen carrier has the same conversion rate, and the temperature is at least 900 ℃ under the condition of not using a light source.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a schematic diagram of a reaction apparatus of a Co-Fe-based photothermal oxygen carrier in photothermal chemical chain hydrogen and synthesis gas according to the invention;
FIG. 2 is an XRD pattern of the Co-Fe-based photo-thermal oxygen carrier prepared in example 1 of the present invention;
FIG. 3 shows the conversion of the reaction under light, 615℃reaction temperature conditions and no light, 615℃reaction temperature conditions;
FIG. 4 is a graph showing the effect of different reaction temperatures on carbon conversion in the presence of light;
FIGS. 5-6 show the variation of the yield and purity of synthesis gas and hydrogen corresponding to different light source current intensities at 615℃reaction temperature;
FIG. 7 is Fe 2 O 3 Powder, co 3 O 4 Powder and Co x Fe y The O oxygen carrier has influence on the yield of synthesis gas and hydrogen under the reaction temperature of 615 ℃ and the illumination condition.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
For a better understanding of the present invention, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present application are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The following description of the embodiments is not intended to limit the preferred embodiments. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the invention may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the ranges, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The invention provides a preparation method of a Co-Fe-based photo-thermal oxygen carrier, which comprises the following steps:
s1, mixing a Co source and a Fe source to obtain a mixture;
and S2, ball milling the mixture, and calcining to obtain the Co-Fe-based photo-thermal oxygen carrier.
The Co-Fe-based photo-thermal oxygen carrier prepared by the method has better photo-thermal chemical chain hydrogen production performance than the oxygen carrier prepared by the traditional sol-gel method; the Co-Fe-based photo-thermal oxygen carrier can be applied to the photo-thermal chemical chain technology for preparing hydrogen, and the temperature of the chemical chain hydrogen is reduced to 615 ℃ (compared with the traditional technology, the same toluene conversion rate is achieved, and the temperature is at least 900 ℃ under the condition of not using a light source).
Specifically, in step S1, in order to facilitate mixing the Co source and the Fe source to obtain a mixture, a small amount of solvent is further added, that is, after mixing the Co source and the Fe source, the solvent is added, and the mixture is obtained by continuing the mixing; solvents used include, but are not limited to, water, ethanol, methanol, and the like.
In some embodiments, the calcination temperature is 900 to 1100 ℃ and the calcination time is 4 to 8 hours.
In some embodiments, in the step of ball milling the mixture, the ball milling speed is 500-700 rpm, the ball milling time is 2-6 h, and the ball-to-material ratio is (4-6): 1; wherein, the ball-to-material ratio refers to the ratio of the mass of the grinding body in the mill to the mass of the material.
In some embodiments, C O The molar ratio of the source to the Fe source is (1-3): 1-4, preferably C O The molar ratio of the source to the Fe source is 1:2.
In some embodiments, the Co source includes, but is not limited to, coO, co 3 O 4 ；
The Fe source includes, but is not limited to, fe 2 O 3 、FeO、Fe 3 O 4 、Fe。
Based on the same inventive concept, the invention also provides a Co-Fe-based photo-thermal oxygen carrier, which is prepared by adopting the preparation method.
Based on the same inventive concept, the invention also provides the Co-Fe-based photo-thermal oxygen carrier prepared by the preparation method or the application of the Co-Fe-based photo-thermal oxygen carrier in the chemical chain reforming coupling hydrogen production and synthesis gas process.
In some embodiments, the above application specifically includes: placing a Co-Fe-based photo-thermal oxygen carrier in a fuel reactor, starting a light source and an electric furnace to heat the fuel reactor, introducing fuel into the fuel reactor after reaching a target temperature, and reacting to obtain synthesis gas;
placing the Co-Fe-based photo-thermal oxygen carrier after the reaction of the fuel reactor in a steam reactor, starting a light source and an electric furnace to heat the fuel reactor, introducing water steam into the steam reactor after reaching a target temperature, and reacting to obtain H 2 。
In some embodiments, the fuel includes toluene and/or water vapor.
In some embodiments, the step of starting the light source and the electric furnace to heat the fuel reactor to a target temperature comprises controlling the current of the light source to be 10-20A and the target temperature to be 400-700 ℃.
In some embodiments, during the step of introducing fuel into the fuel reactor, the flow rate of the fuel is between 0.01 and 0.1mL/min;
and placing the Co-Fe-based photo-thermal oxygen carrier into a fuel reactor, wherein the mass of the Co-Fe-based photo-thermal oxygen carrier is 1-2 g.
Further, referring to FIG. 1, in a fuel reactor, a fuel (e.g., toluene) and lattice oxygen (formed from the Co-Fe-based material of the present applicationThe photo-thermal oxygen carrier is provided) to generate reforming reaction under the illumination condition to prepare synthesis gas, and partial water vapor is possibly introduced according to the situation; in the process of preparing the synthesis gas, the Co-Fe-based photo-thermal oxygen carrier loses lattice oxygen and is reduced to generate a reduced oxygen carrier Co x Fe y O z-δ The method comprises the steps of carrying out a first treatment on the surface of the Then the reduced oxygen carrier Co is added x Fe y O z-δ Placed in a steam reactor, and reduced oxygen carrier Co x Fe y O z-δ Reacts with water vapor to obtain high-concentration hydrogen and reduced oxygen carrier Co x Fe y O z-δ Is oxidized and regenerated to obtain the original Co-Fe-based photo-thermal oxygen carrier (namely the oxidized oxygen carrier Co) x Fe y O z ) The method comprises the steps of carrying out a first treatment on the surface of the Inside the photothermic chain, light enters the fuel reactor and the steam reactor through the glass window, and has an effect on both reforming reaction and steam oxidation reaction.
In some embodiments, in the above application, a proper amount (such as 1-2 g) of Co-Fe-based photo-thermal oxygen carrier is placed in a fuel reactor, a light source and an electric furnace are turned on, the fuel reactor is heated to a preset reaction temperature, nitrogen is introduced to purge the reactor for 5min after the temperature is stable, then toluene and water are introduced, the flow rates of the toluene and the water are 0.025ml/min, and the introduction time is 10min; after the reaction is finished, the toluene is turned off, water vapor is continuously introduced until the hydrogen concentration is reduced to below 0.1%, and the experiment is stopped. The gas concentration was measured using a gas on-line analyzer and the data calculated.
The Co-Fe-based photo-thermal oxygen carrier, the preparation method and the application thereof are further described in the following specific examples. This section further illustrates the summary of the invention in connection with specific embodiments, but should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless specifically stated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
The embodiment of the application provides a preparation method of a Co-Fe-based photo-thermal oxygen carrier, which comprises the following steps:
s1, mixing cobalt oxide powder, ferric oxide powder and ethanol to obtain a mixture;
s2, placing the mixture into a ball mill for ball milling, wherein the ball milling rotating speed is 600rpm, the ball milling time is 4h, and the ball-material ratio is 5:1;
s3, transferring the mixture subjected to ball milling in the step S2 into a baking oven for baking, and then placing the baking oven into a muffle furnace for calcination to obtain the Co-Fe-based photo-thermal oxygen carrier (denoted as Co x Fe y An O oxygen carrier);
wherein the calcination temperature is 1000 ℃ and the calcination time is 6 hours.
Example 2
The embodiment of the application provides the application of the Co-Fe-based photo-thermal oxygen carrier prepared in the embodiment 1 in photo-thermal chemical chain hydrogen production gas and synthesis gas, which specifically comprises the following steps:
placing 1.5g of Co-Fe-based photo-thermal oxygen carrier into a fuel reactor, turning on a light source and an electric furnace, heating the fuel reactor to a preset reaction temperature, introducing nitrogen to purge the reactor for 5min after the temperature is stable, and then starting to introduce toluene and water, wherein the flow rates of the two are 0.025mL/min, and the introduction time is 10min; after the reaction is finished, the toluene is turned off, water vapor is continuously introduced until the hydrogen concentration is reduced to below 0.5%, and the experiment is stopped. The gas concentration was measured using a gas on-line analyzer and the data calculated.
Experimental results
FIG. 2 is an XRD pattern of the Co-Fe-based photo-thermal oxygen carrier prepared in example 1. The spectrum shows that the main component of the Co-Fe-based photo-thermal oxygen carrier is spinel CoFe 2 O 4 。
The reaction conversion was as shown in FIG. 3 under the conditions of 20A light source current at 615℃and no light and 615℃according to the method in example 2. As can be seen from FIG. 3, toluene is converted to CO and H in the presence of light at 615℃reaction temperature 2 、CO 2 Trace of CH 4 And C n Hm followed by steam conversion to high concentration hydrogen; in the absence of light, toluene was hardly reacted and onlySmall amount of CO 2 A gas; however, after the light is added again, toluene can be converted into CO and H 2 、CO 2 Trace of CH 4 And C n H m And the gas has higher conversion rate 92.05 percent (see figure 4).
The effect of different reaction temperatures on carbon conversion was investigated under illumination (20A light source current) according to the method of example 2 and is shown in fig. 4. As can be seen from FIG. 4, the carbon conversion increases with increasing reaction temperature, preferably around 615℃and the synthesis gas ratio is preferably 2.05. The carbon conversion rate refers to the percentage of carbon element in the fuel in the carbon element in the gas product obtained after photochemical chain reforming.
Under the condition of 615 ℃ reaction temperature, the yield and purity of the synthesis gas and the hydrogen corresponding to different light source current intensities are changed, and the results are shown in figures 5-6. Wherein the synthesis gas only calculates CO and H 2 The hydrogen yield was calculated only for H 2 . The synthesis gas yield refers to the amount of synthesis gas obtained after chemical chain reforming of 1kg of oxygen carrier; h 2 The yield is H obtained after photochemical chain reforming of 1kg of the oxygen carrier 2 How much the amount is; syngas purity refers to the percentage of the amount of syngas to the total amount of gas; the hydrogen purity refers to the percentage of the total amount of hydrogen to the total amount of gas.
It can be seen from fig. 5 to 6 that the dependence of the synthesis gas yield on the illumination intensity is not great, and in particular, when the current of the light source is higher than 15.5A, the increase of the current intensity of the light source is not great for the yield increase of synthesis gas. But better for improving the hydrogen yield. The maximum hydrogen yield is 1183mL/g fuel.
Fe was tested separately according to the method in example 2 2 O 3 Powder, co 3 O 4 Powder and Co x Fe y The effect of O oxygen carrier on the yield of synthesis gas and hydrogen under the conditions of 615 ℃ reaction temperature and illumination is shown in figure 7.
From FIG. 7 canTo see the Co prepared in this application x Fe y The O oxygen carrier has remarkable performance in the aspects of preparing synthesis gas and hydrogen.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the Co-Fe-based photo-thermal oxygen carrier is characterized by comprising the following steps of:
mixing a Co source and a Fe source to obtain a mixture;
and ball milling the mixture, and calcining to obtain the Co-Fe-based photo-thermal oxygen carrier.
2. The method for preparing a Co-Fe-based photo-thermal oxygen carrier according to claim 1, wherein the calcination temperature is 900-1100 ℃ and the calcination time is 4-8 hours.
3. The method for preparing a Co-Fe-based photo-thermal oxygen carrier according to claim 1, wherein in the step of ball-milling the mixture, the ball-milling speed is 500-700 rpm, the ball-milling time is 2-6 h, and the ball-to-material ratio is (4-6): 1.
4. The method for preparing a Co-Fe-based photothermal oxygen carrier according to claim 1, wherein the molar ratio of Co source to Fe source is (1-3): 1-4.
5. The method for preparing a Co-Fe-based photothermal oxygen carrier according to any one of claims 1 to 4, wherein the Co source comprises CoO, co 3 O 4 Any one of them;
the Fe comprises Fe 2 O 3 、Fe 3 O 4 Either FeO or Fe.
6. A Co-Fe-based photothermal oxygen carrier, characterized in that it is prepared by the preparation method according to any one of claims 1 to 5.
7. Use of a Co-Fe-based photothermal oxygen carrier prepared by the preparation method according to any one of claims 1 to 5 or a Co-Fe-based photothermal oxygen carrier according to claim 6 in a chemical chain reforming coupling hydrogen production and synthesis gas process.
8. The use of claim 7, comprising: placing a Co-Fe-based photo-thermal oxygen carrier in a fuel reactor, starting a light source and an electric furnace to heat the fuel reactor, introducing fuel into the fuel reactor after reaching a target temperature, and reacting to obtain synthesis gas;
placing the Co-Fe-based photo-thermal oxygen carrier after the reaction of the fuel reactor in a steam reactor, starting a light source and an electric furnace to heat the fuel reactor, introducing water steam into the steam reactor after reaching a target temperature, and reacting to obtain H 2 。
9. The use according to claim 8, wherein the fuel comprises toluene and/or steam;
and (3) starting the light source and the electric furnace to heat the fuel reactor, wherein in the step of reaching the target temperature, the current of the light source is controlled to be 10-20A, and the target temperature is controlled to be 400-700 ℃.
10. The use according to claim 8, wherein in the step of introducing fuel into the fuel reactor, the flow rate of the fuel is 0.01-0.1 mL/min;
and placing the Co-Fe-based photo-thermal oxygen carrier into a fuel reactor, wherein the mass of the Co-Fe-based photo-thermal oxygen carrier is 1-2 g.
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