CN112675853A - Hydrogen-producing oxygen carrier and preparation method and application thereof - Google Patents
Hydrogen-producing oxygen carrier and preparation method and application thereof Download PDFInfo
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- CN112675853A CN112675853A CN202110018620.8A CN202110018620A CN112675853A CN 112675853 A CN112675853 A CN 112675853A CN 202110018620 A CN202110018620 A CN 202110018620A CN 112675853 A CN112675853 A CN 112675853A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000001301 oxygen Substances 0.000 title claims abstract description 77
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 77
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011268 mixed slurry Substances 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 12
- 239000011343 solid material Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 239000000428 dust Substances 0.000 abstract description 11
- 238000005299 abrasion Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000005243 fluidization Methods 0.000 abstract description 7
- 239000013589 supplement Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000969 carrier Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a chemical-looping hydrogen production oxygen carrier, and a preparation method and application thereof, and relates to the technical field of material chemistry. A method for preparing a hydrogen oxygen carrier, comprising: the method comprises the following steps: the ratio of each component in the oxygen carrier to the weight of the oxygen carrier is as follows: fexOy 3‑80％，
MgO 5‑50％；Al2O3Preparing mixed slurry with solid content of 5-60% in 15-70%, wherein the mixed slurry contains an aluminum source, an iron source and a magnesium source, and is acidic; carrying out spray drying on the mixed slurry to obtain a solid material; and (5) roasting the solid material. The hydrogen-producing oxygen carrier is prepared by the preparation method provided by the invention. The particle size of the oxygen carrier is normally distributed, the fluidization performance is excellent, the strength is high, the abrasion is low, a large amount of supplements are not needed in the using process, the dust is less, the requirement on dust removal equipment is low, and the oxygen carrier is suitable for being applied to dust removal equipmentIn the fluidized bed chemical looping hydrogen production reaction.
Description
Technical Field
The invention relates to the technical field of material chemistry, in particular to a hydrogen production oxygen carrier and a preparation method and application thereof.
Background
H2Is an important secondary energy and chemical raw material, has wide application in the aspects of new energy automobiles, petrochemical industry, coal chemical industry, electronic industry, metallurgical industry, food processing, material preparation, organic synthesis, aerospace and the like, and has huge domestic demand. Currently, routes for hydrogen production include methane steam reforming, water electrolysis, coal hydrogen production, and the like, wherein the methane steam reforming hydrogen production and the coal hydrogen production can generate a large amount of greenhouse gas CO2High carbon emission, severe air pollution, prepared H2The purity is not high, and the separation and purification cost is high. Therefore, it is of great significance to find a hydrogen production way with high efficiency, low energy consumption and low carbon emission.
The chemical chain hydrogen production is a novel hydrogen production mode, has high efficiency, high product purity, simple separation and internal separation of CO2Low NO contentxAnd the like, and has wide development prospect.
To fully illustrate the process principle of chemical looping hydrogen production, CH is used4And Fe2O3For example, the reactions occurring in the process were analyzed. The reactions occurring in the whole process are shown in formula (1) to formula (4).
And (3) reduction process:
4Fe2O3+CH4＝8FeO+CO2+2H2O-351.3kJ (1)
steam oxidation process:
3FeO+H2O＝Fe3O4+H271.9kJ (2)
air oxidation process:
4Fe3O4+O2＝6Fe2O3 476kJ (3)
the total process is as follows:
3CH4+2H2O+2O2＝3CO2+8H2 473kJ (4)
the reduction process, the steam oxidation process and the air oxidation process are all accompanied with a great amount of heat absorption and release, and the oxygen carrier is continuously lost. The temperature in the bed layer of the fluidized bed reactor is uniform and easy to control, the fluidized bed reactor is particularly suitable for chemical-looping hydrogen production reaction with high thermal effect, the oxygen carrier can circularly flow among three different reactors (a reduction reactor, a steam oxidation reactor and an air oxidation reactor) to realize the migration of oxygen atoms, and three reaction processes are respectively carried out.
The oxygen carrier needs proper granularity to ensure the stability of a fluidization state when circularly flowing in three fluidized bed reactors, and simultaneously needs higher strength to avoid excessive abrasion in the fluidization process, so that the preparation of the fluidized bed oxygen carrier is one of key technologies of a chemical-looping hydrogen production process.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a hydrogen production oxygen carrier, and a preparation method and application thereof.
The invention is realized by the following steps:
in a first aspect, embodiments of the present invention provide a method for preparing a hydrogen-producing oxygen carrier, comprising:
the ratio of each component in the oxygen carrier to the weight of the oxygen carrier is as follows: fexOy3-80%, wherein
MgO 5-50％；Al2O3Preparing mixed slurry with solid content of 5-60% in 15-70%, wherein the mixed slurry contains an aluminum source, an iron source and a magnesium source, and is acidic;
carrying out spray drying on the mixed slurry to obtain a solid material;
and (5) roasting the solid material.
In an alternative embodiment, the aluminum source is an aluminum sol, and the mixed slurry is obtained by mixing a magnesium source, an iron source and the aluminum sol.
In an alternative embodiment, the mixed slurry is obtained by mixing a magnesium source, an iron source, an aluminum source and nitric acid, wherein the aluminum source is pseudo-boehmite.
In an alternative embodiment, the nitric acid solution has a mass concentration of 0.05% to 5%.
In an alternative embodiment, the magnesium source comprises magnesium oxide;
in an alternative embodiment, the particle size of the magnesium source is less than 1.0 μm.
In an alternative embodiment, the iron source is selected from FeO, Fe2O3And Fe3O4At least one of (1);
in an alternative embodiment, the particle size of the iron source is less than 1.0 μm.
In an alternative embodiment, the firing temperature is 500-.
In a second aspect, the embodiment of the invention provides a hydrogen production oxygen carrier, which is prepared by the preparation method provided by the embodiment of the invention.
In an alternative embodiment, the average particle size of the oxygen carrier is 40-300 μm.
The hydrogen production oxygen carrier provided by the invention is applied to the fluidized bed chemical looping hydrogen production process.
The invention has the following beneficial effects:
the chemical components of the oxygen carrier are reasonably designed, the appropriate solid content of the slurry is controlled in the preparation process, the slurry is controlled to be acidic, and the particle size of the oxygen carrier finally obtained by roasting is normally distributed and the fluidization is excellent by combining spray drying; the prepared aluminum, iron and magnesium composite oxygen carrier has high strength and low abrasion, does not need a large amount of supplements in the using process, has little dust and has low requirement on dust removal equipment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a particle size distribution diagram of an oxygen carrier prepared in example 1;
FIG. 2 is a particle size distribution diagram of an oxygen carrier prepared in example 2;
FIG. 3 is a particle size distribution diagram of an oxygen carrier prepared in example 3;
FIG. 4 is a graph showing the particle size distribution of the oxygen carrier obtained in example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The hydrogen production oxygen carrier provided by the embodiment of the invention, and the preparation method and the application thereof are specifically described below.
The preparation method of the hydrogen production oxygen carrier provided by the embodiment of the invention comprises the following steps:
the ratio of each component in the oxygen carrier to the weight of the oxygen carrier is as follows: fexOy3-80%, wherein
MgO 5-50％；Al2O3Preparing mixed slurry with solid content of 5-60% in 15-70%, wherein the mixed slurry contains an aluminum source, an iron source and a magnesium source, and is acidic;
carrying out spray drying on the mixed slurry to obtain a solid material;
and (5) roasting the solid material.
According to the preparation method provided by the invention, the chemical components of the oxygen carrier are reasonably designed, the appropriate solid content of the slurry is controlled in the preparation process, so that the slurry is acidic, and the particle size of the oxygen carrier finally obtained by roasting is in normal distribution and excellent in fluidization property by combining spray drying; the prepared aluminum, iron and magnesium composite oxygen carrier has high strength and low abrasion, does not need a large amount of supplements in the using process, has little dust and has low requirement on dust removal equipment.
The method comprises the following steps:
and S1, preparing mixed slurry.
The ratio of each component in the oxygen carrier to the weight of the oxygen carrier is as follows: fexOy3-80%, wherein
MgO 5-50％；Al2O3Preparing mixed slurry with solid content of 5-60% in 15-70%, wherein the mixed slurry contains an aluminum source, an iron source and a magnesium source, and the mixed slurry is acidic.
The iron source is selected from FeO and Fe2O3And Fe3O4At least one of (1); preferably, in order to further ensure that the prepared oxygen carrier has a better particle size, the particle size of the iron source is less than 1.0 μm.
The magnesium source comprises magnesium oxide; preferably, the particle size of the magnesium source is less than 1.0 μm.
When the particle size of the iron source and the magnesium source is less than 1.0 mu m, the prepared oxygen carrier can be further ensured to have higher strength and activity.
Specifically, the mixed slurry is a magnesium source, an iron source and an alumina sol which are uniformly mixed by adopting mechanical equipment. Thus obtaining the product.
Or the mixed slurry is obtained by uniformly mixing a magnesium source, an iron source, pseudo-boehmite and nitric acid by adopting mechanical equipment, and the alumina sol is obtained by reacting boehmite with nitric acid. Preferably, the mixed slurry is prepared by adding a magnesium source, an iron source and boehmite into a nitric acid solution with the concentration of 0.05-5%, and uniformly mixing by adopting mechanical equipment.
And S2, spray drying the mixed slurry to obtain a solid material.
S3, roasting the solid material at the temperature of 500-1000 ℃ to obtain the oxygen carrier.
Solid content of the slurry (mass of iron source + mass of magnesium oxide + Al)2O3Mass)/total mass of slurry
Al in alumina sol and pseudo-boehmite2O3And (4) calculating.
The hydrogen-producing oxygen carrier provided by the embodiment of the invention is prepared by adopting the preparation method provided by the invention. Because the oxygen carrier is prepared by the preparation method provided by the invention, the particle size of the oxygen carrier is in normal distribution, and the fluidization performance is excellent; the prepared oxygen carrier has smaller grain diameter than that of the fixed bed, large specific surface area and quick reaction; the oxygen carrier has high strength, low abrasion, no need of a large amount of supplements in the using process, less dust and low requirement on dust removal equipment.
Preferably, the average particle size of the oxygen carrier prepared by the method is 40-300 mu m.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The preparation method of the hydrogen production oxygen carrier provided by the embodiment. The raw materials are as follows:
| raw materials | Quality (g) |
| Fe2O3 | 400 |
| MgO | 226 |
| Aluminium sol ( |
820 |
| H2O | 530 |
Adding water into the alumina sol, stirring uniformly, and then sequentially adding Fe2O3And adding MgO into the diluted aluminum sol to prepare slurry with the solid content of 40%, uniformly stirring the slurry by using a homogenizer, drying by using spray drying equipment, and roasting the dried sample for 8 hours at the temperature of 600 ℃ to obtain the final product.
Example 2
The preparation method of the hydrogen production oxygen carrier provided by the embodiment. The raw materials are as follows:
| raw materials | Quality (g) |
| Fe2O3 | 200 |
| MgO | 400 |
| Aluminium sol ( |
1000 |
| H2O | 2650 |
Adding water into the alumina sol and stirring the mixture evenlyThen sequentially adding Fe2O3And adding MgO into the diluted aluminum sol to prepare slurry with the solid content of 20%, uniformly stirring the slurry by using a homogenizer, drying by using spray drying equipment, and roasting the dried sample for 8 hours at the temperature of 800 ℃ to obtain the final product.
Example 3
The embodiment provides a preparation method of a hydrogen-producing oxygen carrier. The raw materials are as follows:
adding pseudo-boehmite into nitric acid solution with the concentration of 0.5 percent, stirring uniformly to prepare alumina sol, and then sequentially adding Fe3O4、Fe2O3And adding MgO into the prepared alumina sol to prepare slurry with the solid content of 25%, uniformly stirring the slurry by using a homogenizer, drying by using spray drying equipment, and roasting the dried sample for 6 hours at the temperature of 900 ℃ to obtain the final product.
Example 4
The embodiment provides a preparation method of a hydrogen-producing oxygen carrier. The raw materials are as follows:
| raw materials | Quality (g) |
| FeO | 50 |
| |
300 |
| Pseudo-boehmite (solid content 75%) | 1000 |
| 4% nitric acid solution | 9600 |
Adding pseudo-boehmite into a nitric acid solution with the concentration of 4%, uniformly stirring to prepare an aluminum sol, sequentially adding FeO and MgO into the diluted aluminum sol to prepare a slurry with the solid content of 10%, uniformly stirring the slurry by using a homogenizer, drying by using spray drying equipment, and roasting the dried sample for 8 hours at the temperature of 1000 ℃ to obtain the final product.
Comparative example 1
This comparative example is substantially the same as example 3 except that ammonia was used to adjust the slurry pH to 8.5.
Comparative example 2
This comparative example is essentially the same as example 2, except that Fe2O3The addition amount of (2) is 10g, the proportion of the prepared oxygen carrier magnesium oxide is 60.6%, the proportion of the prepared oxygen carrier iron oxide is 1.5%, and the proportion of the prepared oxygen carrier aluminum oxide is 37.9%.
Experimental example 1
The particle size distribution of the oxygen carriers prepared in examples 1 to 4 and comparative examples 1 and 2 was examined. FIGS. 1 to 4 were obtained. As can be seen from fig. 1 to 4, the particle sizes of the oxygen carriers prepared in examples 1 to 4 of the present invention were normally distributed.
Comparative example 1 and comparative example 2, respectively, were not subjected to particle size analysis because the wear index and activity did not meet standards.
Experimental example 2
The oxygen carriers prepared in examples 1-4 and comparative examples 1 and 2 were subjected to strength measurement, and the measurement was carried out by using the measurement (straight tube method) of the abrasion index of the NB/SH/T0964--1The strength of the oxygen carrier is higherLow oxygen carrier consumption, high equipment abrasion and unqualified products. The results are as follows:
| abrasion index AI (% h)-1) | |
| Example 1 | 0.26 |
| Example 2 | 0.43 |
| Example 3 | 0.88 |
| Example 4 | 0.86 |
| Comparative example 1 | 1.78 |
| Comparative example 2 | 0.65 |
Experimental example 3
The oxygen carrier was evaluated in a fluidized bed microreactor with an 8mm internal diameter quartz tube at 900 ℃. CH (CH)4-CO2Air three-stage chemical chain test: the reduction stage used 10ml/min CH4And 90ml/min N2Continuing the reaction until the CO concentration begins to decrease; the purge stage used 90ml/min N2Lasting for 1 min; CO 22The oxidation stage used 10ml/min CO2And 90ml/min N2Continuously reacting until CO is not generated; purging for 1 min; the air oxidation stage uses 10ml/min air and 90ml/min N2For a duration of 3 min. The cycle is carried out 50 times, and H is adopted2The yield is used as an evaluation index of the oxygen carrier. The results are as follows:
it can be seen from the experimental results that the oxygen carriers prepared by the preparation methods provided in examples 1 to 4 of the present invention participate in the hydrogen production reaction, and the hydrogen production reaction effect is better than that of the oxygen carrier prepared in comparative example 2.
In conclusion, the preparation method of the oxygen carrier for hydrogen production provided by the invention has the advantages that the chemical components of the oxygen carrier are reasonably designed, the appropriate solid content of the slurry is controlled in the preparation process, the slurry is controlled to be acidic, and the particle size of the oxygen carrier finally obtained by roasting is normally distributed and the fluidization property is excellent by combining spray drying; the prepared aluminum, iron and magnesium composite oxygen carrier has high strength and low abrasion, does not need a large amount of supplements in the using process, has little dust and has low requirement on dust removal equipment.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of hydrogen-producing oxygen carrier is characterized by comprising the following steps:
the oxygen carrier comprises the following components in percentage by weight: fexOy3-80%, wherein
MgO 5-50％；Al2O3Preparing mixed slurry with solid content of 5-60% in 15-70%, wherein the mixed slurry contains an aluminum source, an iron source and a magnesium source, and the mixed slurry is acidic;
carrying out spray drying on the mixed slurry to obtain a solid material;
and roasting the solid material.
2. The method for preparing the oxygen carrier for hydrogen production according to claim 1, wherein the aluminum source is an aluminum sol, and the mixed slurry is obtained by mixing a magnesium source, an iron source and the aluminum sol.
3. The method for preparing the oxygen carrier for hydrogen production according to claim 1, wherein the mixed slurry is obtained by mixing a magnesium source, an iron source, an aluminum source and a nitric acid solution, and the aluminum source is pseudo-boehmite.
4. The method for preparing the oxygen carrier for hydrogen production according to claim 3, wherein the mass concentration of the nitric acid solution is 0.05-5%.
5. The method of making an oxygen carrier for hydrogen production according to claim 1 wherein the source of magnesium comprises magnesium oxide;
preferably, the particle size of the magnesium source is less than 1.0 μm.
6. The method for preparing an oxygen carrier for hydrogen production according to claim 1, wherein the iron source is selected from FeO and Fe2O3And Fe3O4At least one of (1);
preferably, the particle size of the iron source is less than 1.0 μm.
7. The method for preparing an oxygen carrier for hydrogen production according to claim 1, wherein the calcination temperature is 500-1000 ℃.
8. A hydrogen-producing oxygen carrier, characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. An oxygen carrier according to claim 8, characterized in that its average particle size is 40-300 μm.
10. Use of the hydrogen-producing oxygen carrier of claim 9 in a fluidized bed chemical looping hydrogen production process.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115608364A (en) * | 2022-09-27 | 2023-01-17 | 东南大学 | Oxygen carrier material for hydrogen production by methane chemical looping and large-scale preparation method |
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| WO2012043960A1 (en) * | 2010-09-30 | 2012-04-05 | 한국전력공사 | Oxygen carrier particles and method for manufacturing same |
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