CN111154526B - Composite oxygen carrier for chemical-looping hydrogen production and preparation thereof - Google Patents
Composite oxygen carrier for chemical-looping hydrogen production and preparation thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000001301 oxygen Substances 0.000 title claims abstract description 82
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 82
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 22
- 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 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 41
- 239000003245 coal Substances 0.000 claims description 30
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 24
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011363 dried mixture Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000012512 characterization method Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229910021311 NaFeO2 Inorganic materials 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 238000000034 method Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- 230000002779 inactivation Effects 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000002309 gasification Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 iron-aluminum oxygen Chemical compound 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/06—Catalysts as integral part of gasifiers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a chemical chain hydrogen production methodAn oxygen carrier with high reaction activity and no cyclic deactivation caused by adding alkali K is disclosed2O3/Al2O3NaAlO is added into oxygen carrier2And hydrogen and oxygen carriers are prepared through a chemical chain modulated by alkali metal Na. Adding NaAlO with different mass ratios2In the oxygen carrier subjected to modification, Na0.5Fe4Al6 has better reduction capacity and the unit specific surface area and the pore volume are the highest. Compared with Fe4Al6, the hydrogen production of Na0.5Fe4Al6 is increased by 9.6 percent and reaches 1.47L/g, thus having potential economic value.
Description
Technical Field
The invention relates to an oxygen carrier, in particular to an oxygen carrier for chemical looping hydrogen production, and belongs to the oxygen carrier technology in the field of chemical looping hydrogen production.
Background
The hydrogen is used as clean energy, has the characteristics of high combustion energy and no pollution of products, and is an important raw material in the chemical production process. Coal is the most used fossil fuel and will remain the dominant energy leg for a long period of time in the future. How to directly produce high-quality hydrogen by using coal is widely concerned by society. The traditional coal gasification method can produce hydrogen-rich synthesis gas, but needs to be provided with a pressure swing adsorption device to separate CO and H2And CO2And is accompanied by the emission of greenhouse gases.
Direct chemical looping coal hydrogen production (CLHG) is a method for coupling a coal chemical looping combustion technology with a traditional steam-iron hydrogen production mode. Chemical Looping Combustion (CLC) is a novel flameless combustion mode, the traditional combustion process is divided into two steps of reduction reaction of oxygen carrier in a fuel reactor and oxidation reaction in an air reactor, air is not in direct contact with fuel, and therefore CO is contained in the air reactor2The advantages of internal separation, the CLC process on coal as feedstock, have been extensively studied. The steam-iron process is one of the oldest hydrogen production processes and is used to produce high concentrations of hydrogen. In the fuel reactor, Fe2O3Reduced to FeO and Fe by reaction with fuel, and the gaseous products are steam and CO2:
Fuel+Fe2O3→CO2+H2O+FeO/Fe (1)
In the steam reactor, FeO is steam oxidized and the products are magnetite and hydrogen:
FeO/Fe+H2O→Fe3O4+H2 (2)
in the air reactor, the magnetite is reoxidized to its original form by the oxygen in the airHematite Fe in its starting form2O3:
Fe3O4+O2→Fe2O3 (3)
A large number of researchers have demonstrated the feasibility of gaseous fuels to enable high-concentration hydrogen production through related simulations and experiments. Coal is used as an energy source with richer reserves, and the CLHG process taking coal as a raw material becomes a hot point of research nowadays. Zeng and the like simulate a direct chemical looping hydrogen production process of coal by utilizing Aspen Plus, and the result shows that the CLHG process can convert coal into hydrogen, and compared with the traditional hydrogen production, the thermal efficiency is improved by 30%. Coal is used as solid fuel, and the reaction activity after removing volatile components is low. The alkali metal K is used as a catalyst in the traditional coal gasification process, so that the reaction activity of the coal coke can be improved, and the reaction time is shortened. The increase of the potassium content in the research process of coal CLHG by Zhong et al leads to the increase of the reduction rate of the composite oxygen carrier and obviously improves the reaction activity of the oxygen carrier. However, the volatility of alkali, the inactivation of alkali metal, the low melting point of alkali and the like influence the multi-cycle stability of the alkali. Liu et al investigated potassium-modified Fe2O3/Al2O3The performance of oxygen carriers in direct chemical looping of coal to produce hydrogen was found to remain nearly constant during the first three cycles in a multi-cycle test, after which the carbon conversion and hydrogen yield dropped dramatically as the potassium content in the OCs decreased.
Alkali metal Na as another catalyst which can effectively promote the coal catalytic gasification process has not been studied in the coal CLHG process. The reason may be that conventional Na-containing compounds applied in coal gasification have problems of being easily deactivated and corroding equipment. While NaAlO with high melting point2Can alleviate the above problems compared with NaOH and NaNO3、Na2CO3Etc. NaAlO2The melting point of (A) reached 1650 ℃. The volatilization inactivation of alkali metal is closely related to the melting point, so that the NaAlO with high melting point2Have lower alkali volatility and higher ash melting temperature, and low alkali volatility can mitigate corrosion and fouling problems. At the same time, NaAlO2As NaOH and Al2O3Does not react with Al at high temperatures2O3The reaction is carried out, and the reaction to Si and Al minerals in the coal is possibly more tolerant, which is helpful for relieving the inactivation of the oxygen carrier caused by the coal ash.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a Fe-based catalyst with high reaction activity and capability of avoiding oxygen carrier cyclic inactivation caused by adding alkali metal K, and provides a Fe-based catalyst2O3/Al2O3NaAlO is added into oxygen carrier2And hydrogen and oxygen carriers are prepared through a chemical chain modulated by alkali metal Na.
Compared with the prior art, the invention has the following beneficial effects:
1. the iron-based composite oxygen carrier is prepared by introducing NaAlO2And the addition of Na is adjusted, so that the porosity, the reaction activity and the hydrogen production quality of the iron-aluminum composite oxygen carrier are greatly improved. Secondly, no other alkali metals, such as K, are added to the formulation. NaAlO in the invention2Is added to contribute to Al2O3And Fe2O3Phase separation; while excess NaAlO2Will form Al3Fe5O12The reactivity of the oxygen carrier is reduced. Therefore, the ratio in the present invention is obtained based on a large amount of experimental data, and cannot be easily guessed.
2. The oxygen carrier has very good cycle characteristics, particularly good cycle characteristics of Na0.5Fe4Al6, unsintered surface, carbon conversion rate maintained above 90 percent, and hydrogen production amount greater than 1.40 L.g-1。NaAlO2The addition of the alkali metal is beneficial to improving the reaction performance of the iron-aluminum oxygen carrier, effectively relieves the inactivation caused by the loss of the alkali metal, and avoids the corrosion of equipment.
3. The oxygen carrier is added with NaAlO with different mass ratios2In the modified oxygen carrier, Na0.5Fe4Al6 has better reduction capacity and the highest unit specific surface area and pore volume. The hydrogen production of Na0.5Fe4Al6 is increased by 9.6% compared with Fe4Al6, reaching 1.47L/g.
4. The preparation method is simple, convenient, mild in condition and easy to control. Based on a large amount of creative experimental data, the optimal reaction conditions are obtained, and the reaction conditions are strictly controlled, so that the iron-based composite oxygen carrier with uniform particle size, good dispersion degree and good reaction activity is prepared.
5. The raw materials of the invention are widely available, the preparation method is simple and easy to operate, the invention can be prepared by the sol-gel method, the chemical precipitation method and other methods, the industrial continuous production is convenient to carry out, and the market prospect is good. The direct chemical chain hydrogen production experiment of coal in the fluidized bed can enhance the solid-solid contact between coal and oxygen carrier and raise the carbon conversion rate and reaction rate.
6. The oxygen carrier is applied to a bituminous coal chemical looping gasification process. The reaction with the fuel pyrolysis component is mainly exothermic, so that the energy requirement of solid fuel gasification can be reduced, and the energy consumption is reduced. The deep reduction of the oxygen carrier is also a key step of chemical-looping hydrogen production, and the oxygen carrier can be reduced to FeO and Fe and then can be reacted with H2Reaction of O to Fe3O4And H2And also the rate control process of the whole process.
In order to achieve the purpose, the invention adopts the following technical scheme: an iron-based composite oxygen carrier, characterized in that: NaAlO in oxygen carrier2:Fe2O3:Al2O3The mass ratio of (A) to (B) is 0.1-1:2-10:3-20, preferably 0.5:4:6, 1:4:16, 1.5:4: 16. The oxygen carrier has iron-aluminum crystals with Al3Fe5O12 structure and NaFeO2。
Further, the invention also provides a preparation method of the iron-based composite oxygen carrier, which comprises the following steps:
with Fe (NO)3)3·9H2O、γ-Al2O3As raw material, analytically pure NaAlO2As a modifier, according to NaAlO2:Fe2O3:Al2O3The mass ratio of NaAlO is 0.1-1:2-10:3-20, and NaAlO is weighed2And Fe (NO)3)3·9H2Impregnation of O into gamma-Al2O3Stirring the mixture for 2 hours on a magnetic stirrer at the temperature of 90 ℃, drying the mixture for 12 hours in a drying box at the temperature of 120 ℃, and transferring the dried mixture into a muffle furnace for calcining for 3 hours at the temperature of 900 ℃.
After the oxygen carrier reacts with coal, the reduced product is mainly FeO, and after the oxygen carrier reacts with steam, FeO/Fe reacts with the steam to generate Fe3O4In the presence of Al3Fe5O12Structural iron-aluminum crystal and Al appearing at 35.98 DEG in XRD characterization3Fe5O12The crystal diffraction peak phase separates into two separate Al2O3Characteristic peak and Fe2O3Characteristic peak.
The oxygen carrier prepared by the method has regular and ordered surface particles and high porosity.
Notably, excess NaAlO2The surface of the oxygen carrier is roughened by adding the (B) so as to generate slight melt polymerization and form particles with the diameter of more than 1 mu m to cover the surface of the oxygen carrier. The oxygen carrier of the invention has no excessive NaAlO2The surface of the oxygen carrier is flat, no fusion polymerization exists, and no particles with the diameter larger than 1 mu m cover the surface of the oxygen carrier.
The oxygen carrier is applied to the coal chemical looping to prepare high-quality hydrogen and is applied to the direct coal chemical looping hydrogen preparation in the fluidized bed.
Drawings
FIG. 1 is a drawing of different NaAlO2XRD pattern of addition amount, wherein a is Fe4Al6 b, Na0.5Fe4Al6 c, Na1Fe4Al6 d, and Na1.5Fe4Al6. FIG. 2 is a drawing of different NaAlO2H added with Fe4Al6 oxygen carrier2-TPR spectrum a: fe4Al6 b: Na0.5Fe4Al6 c: na1Fe4Al6 d: Na1.5Fe4Al6. FIG. 3 is H in a multicycle reaction with Na0.5Fe4Al6OC2Yield and overall carbon conversion versus cycle number. Figure 4 is an SEM image of 4 times with the addition of 5% NaAlO2 oxygen carrier. Figure 5 is an SEM image of 8 times with the addition of 5% NaAlO2 oxygen carrier.
Detailed Description
The present invention is further illustrated by the following examples in conjunction with specific embodiments thereof, it is to be understood that these examples are intended only to illustrate the invention and not to limit the scope of the invention, which is defined in the appended claims to the full extent permitted by the skilled artisan after reading the disclosure.
Example 1
Fe (NO3) 3.9H was weighed in a mass ratio of Fe2O3 to Al2O3 of 4:162O, gamma-Al 2O3, adding NO NaAlO2, adding Fe (NO3) 3.9H2Soaking O in gamma-Al 2O3, stirring at 90 deg.C for 2 hr, drying at 120 deg.C in a drying oven for 12 hr, and calcining at 900 deg.C in a muffle furnace for 3 hr. The product is marked as Fe4Al 6.
Example 2
According to NaAlO2:Fe2O3:Al2O3At a mass ratio of 0.5:4:6, Fe (NO3) 3.9H2O、γ-Al2O3、NaAlO2Mixing NaAlO2And Fe (NO)3)3•9H2Impregnation of O into gamma-Al2O3Stirring the mixture for 2 hours on a magnetic stirrer at the temperature of 90 ℃, drying the mixture for 12 hours in a drying box at the temperature of 120 ℃, and transferring the dried mixture into a muffle furnace for calcining for 3 hours at the temperature of 900 ℃. The product is marked as Na0.5Fe4Al6.
Example 3
According to NaAlO2:Fe2O3:Al2O3At a mass ratio of 1:4:16, Fe (NO3) 3.9H2O、γ-Al2O3、NaAlO2Mixing NaAlO2And Fe (NO3) 3.9H2Impregnation of O into gamma-Al2O3Stirring the mixture for 2 hours on a magnetic stirrer at the temperature of 90 ℃, drying the mixture for 12 hours in a drying box at the temperature of 120 ℃, and transferring the dried mixture into a muffle furnace for calcining for 3 hours at the temperature of 900 ℃. The product was noted as Na1Fe4Al 6.
Example 4
According to NaAlO2:Fe2O3:Al2O3At a mass ratio of 1.5:4:16, Fe (NO3) 3.9H2O、γ-Al2O3、NaAlO2Mixing NaAlO2And Fe (NO3) 3.9H2Impregnation of O into gamma-Al2O3Stirring the mixture for 2 hours on a magnetic stirrer at the temperature of 90 ℃, drying the mixture for 12 hours in a drying box at the temperature of 120 ℃, and transferring the dried mixture into a muffle furnace for calcining for 3 hours at the temperature of 900 ℃. The product is marked as Na1.5Fe4Al6.
Characterization of the results of examples 1-4
(1)NaAlO2Influence of the additive amount on the coal-direct chemical looping hydrogen production (CLHG) process
FIG. 1 is a drawing of different NaAlO2The XRD spectrum a of the added amount is Fe4Al6 b, Na0.5Fe4Al6 c, Na1Fe4Al6 d and Na1.5Fe4Al6. FIG. 1 shows different NaAlO2In the XRD spectrum of the added oxygen carrier OC, the independent diffraction peak of Na is not detected in XRD because the added amount of Na is less. Graph a shows that in the Fe4Al6 oxygen carrier, Al is mainly formed3Fe5O12Iron-aluminium crystals of a structure which would hinder Fe2O3Reducing the oxygen carrier to reduce the reactivity of the oxygen carrier. b shows that when 5% NaAlO is added2At 35.98 ℃ Al3Fe5O12The crystal diffraction peak phase separates into two separate Al2O3Characteristic peak and Fe2O3Characteristic peaks, probably due to the addition of NaAlO2After that, a small amount of NaFeO is formed2. Adding 10% and 15% NaAlO2In the meantime, the phenomenon of complaints did not occur, but more Al was formed3Fe5O12And (4) crystals.
(2)NaAlO2Addition amount of Fe2O3/ Al2O3The unit hydrogen consumption of the oxygen carrier.
TABLE 1 different NaAlO2Addition amount of Fe2O3/ Al2O3Unit hydrogen consumption of oxygen carrier
FIG. 2 is a drawing of different NaAlO2H added with Fe4Al6 oxygen carrier2-TPR spectrum a: fe4Al6
b: Na0.5Fe4Al6 c: na1Fe4Al6 d: Na1.5Fe4Al6. Because the peak appearance of the high-temperature region is not complete, and the experiment in the fluidized bed also proves that Fe2O3After being reduced to FeO, the reduction is more difficult to continue, so that the oxygen consumed by the reaction is mainly derived from Fe2O3→Fe3O4And Fe3O4→ oxygen consumed by both peaks of FeO. FIG. 2 is H of oxygen carrier reduction process2TPR analysis, from which it can be seen that the first reduction peak of the Fe4Al6 oxygen carrier appears at 480-The second reduction peak occurs at 740 ℃. When NaAlO is added2Later, the time at which the first reduction peak occurred was shifted backwards, indicating that NaAlO2Resulting in Fe2O3→Fe3O4Is inhibited. And the second peak follows NaAlO2The increase in the amount of addition advances the peak position and contributes to Fe3O4Is reduced to FeO. Table 1 shows the results for H2The TPR curve is treated to obtain the unit hydrogen consumption of each sample, and the table shows that the unit hydrogen consumption of Na0.5Fe4Al6 is higher, Na0.5Fe4Al6 has better oxygen release performance, and 10 percent and 15 percent of NaAlO are added2The reducing ability of (a) is decreased. This is consistent with the change in the reaction performance of OC during the CLHG reaction carried out in the fluidized bed.
TABLE 2 BET analysis of the different oxygen carriers
(3) Multiple cycle stability test
FIG. 3 is H in a multicycle reaction with Na0.5Fe4Al6OC2Yield and overall carbon conversion versus cycle number. To investigate NaAlO2As a stability of the alkali metal additive in the multi-cycle reaction process, 8 redox cycle experiments were performed in the fluidized bed reactor. FIG. 3 shows carbon conversion and cumulative H in a multi-cycle experiment2Yield versus number of redox cycles. H2The yield and carbon conversion are relatively stable during 8 redox cycles, the carbon conversion is maintained above 90%, and the hydrogen yield is greater than 1.40L/g. The oxygen carrier added with sodium metaaluminate has no inactivation phenomenon and has good cycle stability.
In a word, the coal-direct chemical looping hydrogen production (CLHG) couples the coal chemical looping combustion process with the steam-iron reaction process, realizes high-efficiency hydrogen production and simultaneously achieves CO capture2The purpose of (1) is a very promising hydrogen production mode. Coal and Fe in a fluidized bed2O3/Al2O3Experiment of oxygen carrier with different mass ratiosStudy of the conversion of carbon by COAL/OC and H2Yield and OC reduction. By adding NaAlO2For Fe2O3/Al2O3And (3) modifying, and researching the influence of alkali metal Na on the direct chemical looping hydrogen production process of coal and the circulation stability of OC. The results show that the carbon conversion rate and the hydrogen production efficiency are highest when the mass ratio of the coal to the Fe4Al6 is 0.05, and OC can only be reduced to Fe2+. Adding NaAlO with different mass ratios2Among the oxygen carriers subjected to modification, Na0.5Fe4Al6 has the best reduction capacity and the highest unit specific surface area and pore volume. The hydrogen production of Na0.5Fe4Al6 is increased by 9.6% compared with Fe4Al6, reaching 1.47L/g. Proper amount of NaAlO2Is added to contribute to Al2O3And Fe2O3Phase separation; while excess NaAlO2Will form Al3Fe5O12The reactivity of the oxygen carrier is reduced. Good Na0.5Fe4Al6 cycle characteristics, unsintered surface, carbon conversion rate of more than 90 percent and hydrogen production of more than 1.40L g-1。NaAlO2The addition of the alkali metal is beneficial to improving the reaction performance of the iron-aluminum oxygen carrier, effectively relieves the inactivation caused by alkali metal loss, avoids equipment corrosion and is a very potential alkali metal additive.
FIGS. 4 and 5 are the addition of 5% NaAlO2SEM images after 4 and 8 cycles of oxygen carrier. In order to examine the stability of the oxygen carrier, the oxygen carrier after 4 times and 8 times of circulation is analyzed by a scanning electron microscope. As can be seen from the figure, after multiple cycles, the surface appearance of the oxygen carrier is not greatly changed, the particles on the surface of the oxygen carrier are still regular and ordered, the pores are not blocked, and even the phenomena of pore deepening and pore increasing occur. The surface particles appeared to agglomerate slightly, but large particles exceeding 1 μm were not formed. This indicates that the na0.5fe4al6 oxygen carrier has good sintering resistance during cycling.
Claims (3)
1. A composite oxygen carrier for chemical looping hydrogen production is characterized in that the oxygen carrier is made of Fe2O3/Al2O3For the matrix, NaAlO is introduced by wet impregnation2A modifying agent; the oxygen carrier is not added with other alkali metals except Na; NaAlO in the oxygen carrier2:Fe2O3:Al2O3The mass ratio is 0.5:4:6, 1:4:16, 1.5:4: 16; the oxygen carrier has Al3Fe5O12Structural iron-aluminum crystals in the presence of NaFeO2;
After the oxygen carrier reacts with coal, the reduced product is mainly FeO, and after the oxygen carrier reacts with steam, FeO/Fe reacts with the steam to generate Fe3O4In the presence of Al3Fe5O12Structural iron-aluminum crystal and in XRD characterization, Al appears after reaction2O3Characteristic peak and Fe2O3A characteristic peak;
the preparation method of the oxygen carrier comprises the following steps:
with Fe (NO)3) 3•9H2O、γ-Al2O3As raw material, analytically pure NaAlO2Weighing NaAlO by mass as modifier2And Fe (NO)3) 3•9H2Impregnation of O into gamma-Al2O3Stirring the mixture for 2 hours on a magnetic stirrer at the temperature of 90 ℃, drying the mixture for 12 hours in a drying box at the temperature of 120 ℃, and transferring the dried mixture into a muffle furnace for calcining for 3 hours at the temperature of 900 ℃.
2. The composite oxygen carrier for chemical looping hydrogen production according to claim 1, characterized in that the surface particles of the oxygen carrier are regularly ordered and have high porosity; the oxygen carrier is free of excessive NaAlO2The surface of the oxygen carrier is flat, no fusion polymerization exists, and no particles with the diameter larger than 1 mu m cover the surface of the oxygen carrier.
3. The composite oxygen carrier for chemical looping hydrogen production according to claim 1, characterized in that the oxygen carrier is applied to coal chemical looping hydrogen production.
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