WO2022160487A1 - 一种改性镍铁复合氧载体及其制备方法和应用 - Google Patents

一种改性镍铁复合氧载体及其制备方法和应用 Download PDF

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WO2022160487A1
WO2022160487A1 PCT/CN2021/089766 CN2021089766W WO2022160487A1 WO 2022160487 A1 WO2022160487 A1 WO 2022160487A1 CN 2021089766 W CN2021089766 W CN 2021089766W WO 2022160487 A1 WO2022160487 A1 WO 2022160487A1
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oxygen carrier
composite oxygen
nickel
iron composite
oxide
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French (fr)
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王训
付根深
许婷婷
肖波
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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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
    • B01J23/755—Nickel
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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

Definitions

  • the invention belongs to the technical field of chemical chain combustion oxygen carriers, and particularly relates to a modified nickel-iron composite oxygen carrier and a preparation method and application thereof.
  • Hydrogen energy is an ideal secondary energy carrier.
  • the main product of combustion in the air is water, which does not cause any environmental pollution. It has become an important direction of energy development in the world.
  • hydrogen production at home and abroad mainly comes from the reforming process of fossil fuels, and its preparation needs to go through processes such as gas purification, synthesis gas reforming, shift and pressure swing adsorption. This method is not only complicated in process, but also has high energy consumption and low hydrogen production efficiency.
  • the value of syngas itself is ignored, such as combustion for heat supply, power generation, or the preparation of high-value fuels such as ethanol through Fischer-Tropsch synthesis.
  • the chemical chain technology is a new way of efficient conversion and utilization of energy.
  • Bio-oil as a form of biomass energy with high energy density and easy storage, has received extensive attention in recent years. However, bio-oil is directly hydrogenated to produce biodiesel, and it is used for chemical chain hydrogen production or synthesis gas, which faces the phenomenon of low hydrogen purity, deactivation of oxygen carrier, agglomeration and sintering.
  • the present invention provides a modified nickel-iron composite oxygen carrier, which improves the structural stability of the oxygen carrier by doping with modifiers such as cerium oxide, aluminum oxide, and zirconium oxide.
  • the quality of the synthesis gas and hydrogen prepared is further improved, and the material defect of the nickel-iron composite oxygen carrier with poor circulation performance is solved at the same time.
  • the modified nickel-iron composite oxygen carrier can be obtained by calcining the body at 900-1000° C. for 6-9 hours, and the modifier is a mixture of one or more of ceria, alumina and zirconia.
  • the modifier is cerium oxide.
  • the mass ratio of the nickel oxide, ferric oxide and the modifier is (15-25): (50-60): (15-25), preferably, the nickel oxide and the three The mass ratio of ferrous oxide is 1:4.
  • the temperature of constant temperature drying is 100-120°C, and the drying time is 6-9h.
  • the nickel oxide, the ferric oxide and the modifier are uniformly mixed by ball milling.
  • a modified nickel-iron composite oxygen carrier is provided, which is prepared according to the aforementioned preparation method.
  • an application of the modified nickel-iron composite oxygen carrier is provided, and the application is an application of coupling hydrogen production and synthesis gas based on chemical chain technology.
  • the modified nickel-iron composite oxygen carrier is mixed with bio-oil and reacted to obtain the modified nickel-iron composite oxygen carrier and synthesis gas in a reduced state;
  • water vapor is also added in the step (1), and the ratio of the liquid volume of the water vapor to the liquid volume of the bio-oil is 1.2-2.
  • the reaction temperature of the step (1), step (2) and step (3) is 900°C
  • the bio-oil is obtained by pyrolysis of organic solid waste
  • the synthesis gas is a mixed gas of CO and H2 .
  • a modifier is added on the basis of the patent application CN202011629463.6 to improve the structural stability of the oxygen carrier.
  • the addition of CeO 2 leads to the formation of Ce-Fe-O solid solution and perovskite structure CeFeO 3 , which has higher redox activity; at the same time, it has a good supporting effect on the stable existence of NiFe 2 O 4 structure, thus effectively The sintering phenomenon caused by the collapse of the pore structure is prevented, the quality of the prepared synthesis gas and hydrogen is further improved, and the material defect of poor cyclic performance of the nickel-iron composite oxygen carrier is solved.
  • the modified nickel-iron composite oxygen carrier of the present invention has higher activity, stronger target product selectivity, more prominent hydrogen production capacity, the prepared synthesis gas has a purity of 81%, and the synthesis gas yield is further improved to 2.01Nm 3 / kg (bio-oil), the purity of hydrogen is as high as 95%, and the hydrogen yield is increased to 0.724Nm 3 /kg (bio-oil), and there are no negative effects such as oxygen carrier performance decline and hydrogen yield decline in multiple cycles.
  • FIG. 1 is the XRD patterns of the composite oxygen carriers prepared in Examples 1-3 of the present invention and Comparative Example 1.
  • FIG. 1 is the XRD patterns of the composite oxygen carriers prepared in Examples 1-3 of the present invention and Comparative Example 1.
  • Example 3 is a SEM image of the composite oxygen carrier prepared in Example 1 of the present invention.
  • Example 4 is a SEM image of the composite oxygen carrier prepared in Example 2 of the present invention.
  • Example 5 is a SEM image of the composite oxygen carrier prepared in Example 3 of the present invention.
  • Fig. 6 is the test chart of the synthesis gas yield of application examples 1.1-1.4.
  • Fig. 7 is the hydrogen purity test chart of application examples 1.1-1.4.
  • Fig. 8 is the XRD test chart of the phase structure of the bio-oil reduction stage of application examples 1.1-1.4.
  • Fig. 9 is the test chart of the synthesis gas yield of application examples 2.1-2.4.
  • Fig. 10 is the hydrogen purity test chart of application examples 2.1-2.4.
  • Figure 11 is the XRD pattern of the composite oxygen carrier after 5 cycles of application examples 2.1-2.4.
  • Figure 12 is the SEM image of the composite oxygen carrier after 5 cycles of application example 2.4.
  • Figure 13 is the SEM image of the composite oxygen carrier after 5 cycles of Application Example 2.1.
  • Figure 14 is the SEM image of the composite oxygen carrier after 5 cycles of Application Example 2.2.
  • Figure 15 is the SEM image of the composite oxygen carrier after 5 cycles of application example 2.3.
  • a CeO 2 modified nickel-iron composite oxygen carrier is prepared by the following method:
  • Ni15Fe60Ce25 composite oxygen carrier a nickel-iron composite oxygen carrier
  • a ZrO 2 modified nickel-iron composite oxygen carrier is prepared by the following method:
  • NiO nickel oxide
  • Fe 2 O 3 iron oxide
  • ZrO 2 zirconia
  • Ni15Fe60Zr25 composite oxygen carrier (2) Pour the solution in the ball mill into a beaker, dry it in a constant temperature drying oven at 105°C for 6 hours, evaporate excess solvent water to obtain a precursor, put the precursor into a muffle furnace, and calcine it at 900°C for 6 hours hours, the nickel-iron composite oxygen carrier was obtained, which was denoted as Ni15Fe60Zr25 composite oxygen carrier.
  • An Al 2 O 3 modified nickel-iron composite oxygen carrier is prepared by the following method:
  • NiO nickel oxide
  • Fe 2 O 3 iron oxide
  • Al 2 O 3 alumina
  • Ni15Fe60Al25 composite oxygen carrier (2) Pour the solution in the ball mill into a beaker, dry it in a constant temperature drying oven at 105°C for 6 hours, evaporate excess solvent water to obtain a precursor, put the precursor into a muffle furnace, and calcine it at 900°C for 6 hours hours, a nickel-iron composite oxygen carrier is obtained, which is denoted as Ni15Fe60Al25 composite oxygen carrier.
  • Ni20Fe80 composite oxygen carrier (2) Pour the solution in the ball mill into a beaker, dry it in a constant temperature drying oven at 105°C for 6 hours, evaporate excess solvent water to obtain a precursor, put the precursor in a muffle furnace, and calcine at 900°C for 6 hours , to obtain a nickel-iron composite oxygen carrier, denoted as Ni20Fe80 composite oxygen carrier.
  • XRD test test The oxygen carriers prepared in Examples 1-3 and Comparative Example 1 were subjected to XRD test, and the test results are shown in FIG. 1 .
  • the oxygen carriers modified by the three metals all have three crystal phase structures of Fe 2 O 3 , NiFe 2 O 4 and NiO, and the positions of the peaks are basically the same, which indicates that the doping of the modified metal has an effect on Ni/O.
  • the formation of the structure between Fe has no effect; in addition, the phases of CeO 2 , Al 2 O 3 and ZrO 2 exist independently, and do not form a new phase structure with NiO or Fe 2 O 3 at high temperature during the preparation process .
  • the first set of application examples In a fixed-bed tubular reactor, the oxygen carrier is passed into bio-oil successively to prepare synthesis gas, and then steam is used to prepare hydrogen, as described below.
  • the carrier gas flow rate (air, nitrogen) is 500ml/min; the unit of time interval for chromatographic recording of tail gas components is seconds, and the content of each component in the tail gas is calculated on the basis of 500ml/min nitrogen.
  • the carrier gas flow rate (air, nitrogen) is 500ml/min; the unit of time interval for chromatographic recording of tail gas components is seconds, and the content of each component in the tail gas is calculated on the basis of 500ml/min nitrogen.
  • the hydrogen purity test will be carried out in application examples 1.1-1.4, and the test results are shown in FIG. 7 . It can be seen from Figure 7 that the purity and yield of hydrogen on the Ni15Fe60Ce25 modified oxygen carrier are further improved compared with the Ni20Fe80 oxygen carrier. This is because there is also a positive synergy between Fe 2 O 3 and CeO 2 , and even a simple physical contact can improve the reducibility of Fe 2 O 3 ; in addition, the formation of Fe-Ce solid solution and the perovskite CeFeO 3 The occurrence of oxygen vacancies will greatly promote the generation of oxygen vacancies and accelerate the migration of lattice oxygen from the interior of the oxygen carrier to the surface.
  • Ni15Fe60Zr25 oxygen carrier showed a decrease in hydrogen purity and yield, which may be caused by the addition of the inert carrier ZrO 2 , which reduced the content of the active component NiFe 2 O 4 and reduced the reduction of Fe 2 O 3 .
  • the hydrogen production ability of Ni15Fe60Al25 oxygen carrier we found that its hydrogen yield and purity are abnormally low, which is due to the formation of inert spinel FeAl 2 O 4 during the reaction process, and this structure is not conducive to Fe Further reduction and oxidation of elements.
  • the XRD test was carried out on the phase structure of the bio-oil reduction stage of application examples 1.1-1.4, and the test results are shown in FIG. 8 .
  • the reduced Ni15Fe60Ce25 oxygen carrier has a perovskite structure CeFeO 3 .
  • the Ni15Fe60Ce25 oxygen carrier has higher hydrogen yield and syngas yield, which is related to the appearance of this structure.
  • Ni15Fe60Zr25 oxygen carrier has a large amount of Fe 3 O 4 structure after the reduction of bio-oil, which may be due to the addition of the inert carrier ZrO 2 , which leads to the reduction of NiFe 2 O 4 inside the oxygen carrier, thereby improving the reduction difficulty of Fe 2 O 3 in disguise . But it can be seen that ZrO 2 does not change in the reaction stage, which also proves that its own thermal stability is very good.
  • AlFe 2 O 4 belongs to the high temperature phase, that is, it can only exist above 860 °C, and it is formed by the mutual dissolution of Fe 3 O 4 and FeAl 2 O 4 at high temperature.
  • FeAl 2 O 4 is very stable, and due to thermodynamic limitations, FeAl 2 O 4 hardly reacts with water vapor below 1123K, and the formation of AlFe 2 O 4 will greatly reduce the thermodynamic driving force of the redox reaction. The hydrogen capacity is significantly reduced.
  • the application examples 2.1-2.4 will be tested for 5 cycles of synthesis gas yield, and the test results are shown in FIG. 9 .
  • the Ni15Fe60Ce25 oxygen carrier has the same yield of synthesis gas in 5 cycles, and the synthesis gas purity is maintained at about 81%; the synthesis gas yield of Ni15Fe60Zr25 oxygen carrier is the same, and the synthesis gas purity increases slightly with the increase of the number of cycles.
  • the two modified oxygen carriers, Ni15Fe60Ce25 and Ni15Fe60Zr25 have higher synthesis gas purity and yield than Ni20Fe80 in multiple cycles.
  • the yield and purity of Ni15Fe60Al25 oxygen carrier synthesis gas increased with the increase of cycle times.
  • Ni15Fe60Ce25 not only has the highest hydrogen yield but also the hydrogen purity has been maintained at about 96%, and the performance of hydrogen and syngas production has been further improved, while showing excellent cycle stability. sex. This indicates that the doping of CeO 2 and the formation of perovskite CeFeO 3 ensure the cycling stability of oxygen carriers.
  • Ni15Fe60Zr25 also showed excellent cycle stability during 5 cycles. This is because ZrO2 has stronger structural stability and can ensure that the pore structure of the oxygen carrier does not change significantly during multiple cycles, thereby ensuring that the lattice oxygen is stable. The release rate is stable. However, the hydrogen yield and purity of Ni15Fe60Zr25 are relatively low, because ZrO 2 does not participate in the reaction, and the structure of NiFe 2 O 4 decreases with the decrease of the relative mass fraction of Fe 2 O 3 , thus reducing the reducibility of Fe in the oxygen carrier.
  • the obvious reduction of the hydrogen production capacity of the Ni15Fe60Al25 oxygen carrier is caused by the formation of two inert spinel structures, FeAl 2 O 4 and AlFe 2 O 4 during the reaction process, which has been obtained from the XRD characterization analysis in the previous section. confirmed.
  • the hydrogen production capacity of the Ni15Fe60Al25 oxygen carrier decreased significantly again, but the hydrogen yield was relatively stable in the subsequent cycles, and the hydrogen purity was maintained at about 85%.
  • This also shows the stability of the structure of FeAl 2 O 4 and AlFe 2 O 4 from the side, which greatly alleviates the sintering phenomenon of Fe element during the reduction process.
  • Ni15Fe60Ce25 is the best modified oxygen carrier.
  • the composite oxygen carrier after 5 cycles of application examples 2.1-2.4 was tested by SEM, and the test results are shown in Figures 12-15.
  • the Ni20Fe80 oxygen carrier has obvious pore structure collapse, and the surface agglomeration phenomenon is obvious, while the structure of the three modified oxygen carriers Ni15Fe60Ce25, Ni15Fe60ZrO2, Ni15Fe60Al25 is still stable, which shows that the addition of the three modified metals has the cycle stability of the oxygen carrier played a positive role.
  • the pore structure of Ni15Fe60Ce25 oxygen carrier is more obvious, which is favorable for the release of lattice oxygen, and also proves the above related test results.

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Abstract

本发明属于化学链燃烧氧载体技术领域，具体涉及一种改性镍铁复合氧载体及其制备方法和应用。本发明制备方法将氧化镍，三氧化二铁和改性剂加水混合均匀后干燥得到前驱体，将前驱体在900-1000℃煅烧6-9h，即可获得改性镍铁复合氧载体，所述改性剂为氧化铈、氧化铝、氧化锆中的一种或多种的混合。本发明在专利申请的基础上加入改性剂，改善氧载体的结构稳定性，具有更高的氧化还原活性，进一步提高制备的合成气及氢气品质，同时解决镍铁复合氧载体循环性能差的材料缺陷，制备方法同样简单易行，有利于大规模生产应用。

Description

一种改性镍铁复合氧载体及其制备方法和应用 【技术领域】
本发明属于化学链燃烧氧载体技术领域，具体涉及一种改性镍铁复合氧载体及其制备方法和应用。
【背景技术】
氢能是一种理想的二次能源载体，在空气中燃烧主要产物为水，不造成任何环境污染，已然成为世界上能源发展的重要方向。但是目前国内外制氢主要来源于化石燃料的重整工艺，其制备需要经历气体净化、合成气重整、变换和变压吸附等过程。这种方式不仅工艺复杂，而且能耗高，制氢效率低；同时合成气自身的价值被忽视，如燃烧供热、发电，或通过费托合成制备乙醇等高值燃料等。化学链技术是一种能源高效转化利用的新方式，通过不同反应器之间的耦合串联，可实现高纯氢和高纯合成气的制备。生物油作为一种能量密度高，易储存的生物质能源形式，近些年来得到了广泛的关注。但生物油直接加氢制生物柴油，用于化学链制氢或合成气则面临氢气纯度低，氧载体失活，团聚烧结等现象。
本申请的发明人在先前提交的专利申请CN202011629463.6，一种镍铁复合氧载体及其制备方法和应用，提出了一种镍体复合氧载体的制备和应用，实现了高纯氢与合成气的共制备，其中合成气的纯度接近80％，且H 2/CO比为2；氢气的纯度也高达95％以上，完全满足工业化应用，大大促进了生物油高值化利用。但是在后续进一步的研究中发现，这种镍体复合氧载体在多次循环过程中出现了明显的烧结和团聚现象，氢气产率及纯度出现了明显的下跌，其结构稳定性遭到破坏，不利用长期的使用。
因此，还需要对镍铁复合氧载体的进一步改性优化。
【发明内容】
针对现有技术的以上缺陷或改进需求，本发明提供了一种改性镍铁复合氧载体，通过氧化铈、氧化铝、氧化锆等改性剂的掺杂，改善氧载体的结构稳定性，进一步提高制备的合成气及氢气品质，同时解决镍铁复合氧载体循环性能差的材料缺陷。
为实现上述目的，按照本发明的一个方面，提供了一种改性镍铁复合氧载体的制备方法，将氧化镍，三氧化二铁和改性剂加水混合均匀后干燥得到前驱体，将前驱体在900-1000℃煅烧6-9h，即可获得改性镍铁复合氧载体，所述改性剂为氧化铈、氧化铝、氧化锆中的一种或多种的混合。
作为优选，所述改性剂为氧化铈。
作为优选，所述氧化镍、三氧化二铁和改性剂的质量之比为(15-25)：(50-60)：(15-25),优选的，所述氧化镍与所述三氧化二铁的质量比为1:4。
作为优选，恒温干燥的温度为100-120℃，干燥时间为6-9h。
作为优选，所述氧化镍，所述三氧化二铁和所述改性剂是通过球磨混合均匀。
按照本发明的另一方面，提供了一种改性镍铁复合氧载体，根据前面所述的制备方法制备而成。
按照本发明的另一方面，提供了改性镍铁复合氧载体的应用，所述应用为基于化学链技术耦合制氢与合成气的应用。
作为优选，包括以下步骤：
(1)将改性镍铁复合氧载体与生物油混合后反应，获得还原态的改性镍铁复合氧载体和合成气；
(2)将还原态的改性镍铁复合氧载体与水蒸气反应，获得氢气，还原态的改性镍铁复合氧载体得到部分氧化；
(3)部分氧化后的改性镍铁复合氧载体通过空气彻底氧化，完成再生。
作为优选，所述步骤(1)中还加入了水蒸气，所述水蒸汽的液体体积与生物油的液体体积之比值为1.2-2。
作为优选，所述步骤(1)，步骤(2)和步骤(3)的反应温度为900℃，所述生物油为有机固废热解而成，所述合成气为CO和H2的混合气体。
本发明的有益效果有：
(1)本发明在专利申请CN202011629463.6的基础上加入改性剂，改善氧载体的结构稳定性。其中CeO 2的加入导致Ce-Fe-O固溶体以及钙钛矿型结构CeFeO 3的生成，具有更高的氧化还原活性；同时对NiFe 2O 4结构的稳定存在具有很好的支撑作用，从而有效防止孔隙结构坍塌而带来的烧结现象，制备的合成气及氢气品质得到进一步的提高，解决镍铁复合氧载体循环性能差的材料缺陷，制备方法同样简单易行，有利于大规模生产应用。
(2)本发明改性镍铁复合氧载体活性更高，目标产物选择性跟更强，制氢能力更突出，制备的合成气纯度达到81％，合成气产率进一步提升至2.01Nm 3/kg(生物油)，氢气的纯度高达95％，氢气产率提升至0.724Nm 3/kg(生物油)，在多次循环中未出现氧载体性能下降，氢气产率下跌等负面影响。
(3)本发明的改性镍铁复合氧载体在共制备氢与合成气中的应用，与现有的化学链技术及先前专利相比，不仅克服了生物油在化学链技术中应用缺陷，促进生物油更加高值化利用，同时长期循环使用中展现了优异的稳定性，更加符合工业的实际应用。
【附图说明】
图1是本发明实施例1-3和对比实施例1制备的复合氧载体XRD图。
图2是本发明对比实施例1制备的复合氧载体SEM图。
图3是本发明实施例1制备的复合氧载体SEM图。
图4是本发明实施例2制备的复合氧载体SEM图。
图5是本发明实施例3制备的复合氧载体SEM图。
图6是应用实施例1.1-1.4合成气产率测试图。
图7是应用实施例1.1-1.4氢气纯度测试图。
图8是应用实施例1.1-1.4生物油还原阶段物相结构XRD测试图。
图9是应用实施例2.1-2.4合成气产率测试图。
图10是应用实施例2.1-2.4氢气纯度测试图。
图11是应用实施例2.1-2.4经过5次循环后的复合氧载体XRD图。
图12是应用实施例2.4经过5次循环后的复合氧载体SEM图。
图13是应用实施例2.1经过5次循环后的复合氧载体SEM图。
图14是应用实施例2.2经过5次循环后的复合氧载体SEM图。
图15是应用实施例2.3经过5次循环后的复合氧载体SEM图。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例
实施例1
一种CeO 2改性镍铁复合氧载体，通过以下方法制备而成：
(1)称取15g的氧化镍(NiO)粉末，60g的氧化铁(Fe 2O 3)粉末，25g氧化铈(CeO 2)粉末一起倒入球磨罐内，然后向罐内加入200ml去离子水，以300r/min的转速，球磨2小时。
(2)将球磨罐中的溶液倒入烧杯，在105℃的恒温干燥箱内，干燥6h，蒸发多余的溶剂水得到前驱体，将前驱体放入马弗炉内，900℃下煅烧6小时，得到镍铁复合氧载体，记为Ni15Fe60Ce25复合氧载体。
实施例2
一种ZrO 2改性镍铁复合氧载体，通过以下方法制备而成：
(1)称取15g的氧化镍(NiO)粉末，60g的氧化铁(Fe 2O 3)粉末，25g氧化锆(ZrO 2)粉末一起倒入球磨罐内，然后向罐内加入200ml去离子水，以300r/min的转速，球磨2小时。
(2)将球磨罐中的溶液倒入烧杯，在105℃的恒温干燥箱内，干燥6h，蒸发多余的溶剂水，得到前驱体，将前驱体放入马弗炉内，900℃下煅烧6小时，得到镍铁复合氧载体，记为Ni15Fe60Zr25复合氧载体。
实施例3
一种Al 2O 3改性镍铁复合氧载体，通过以下方法制备而成：
(1)称取15g的氧化镍(NiO)粉末，60g的氧化铁(Fe 2O 3)粉末，25g氧化铝(Al 2O 3)粉末一起倒入球磨罐内，然后向罐内加入200ml去离子水，以300r/min的转速，球磨2小时。
(2)将球磨罐中的溶液倒入烧杯，在105℃的恒温干燥箱内，干燥6h，蒸发多余的溶剂水，得到前驱体，将前驱体放入马弗炉内，900℃下煅烧6小时，得到镍铁复合氧载体，记为Ni15Fe60Al25复合氧载体。
对比实施例1
(1)称取20g的氧化镍(NiO)粉末，80g的氧化铁(Fe 2O 3)粉末，一起倒入球磨罐内，然后向罐内加入200ml去离子水，以300r/min的转速，球磨2小时。
(2)将球磨罐中的溶液倒入烧杯，在105℃的恒温干燥箱内，干燥6h，蒸发多余的溶剂水得到前驱体，将前驱体放入马弗炉内，900℃下煅烧6小时，得到镍铁复合氧载体，记为Ni20Fe80复合氧载体。
测试实施例
1.XRD测试测试。将实施例1-3和对比实施例1制备的氧载体进行XRD测试，测试结果如图1所示。三种金属改性后的氧载体与Ni20Fe80一样，都存在Fe 2O 3、NiFe 2O 4、NiO三种晶相结构，且峰的位置基本一致，这说明 改性金属的掺杂对Ni/Fe之间结构的形成并不产生影响；此外CeO 2,Al 2O 3,ZrO 2的物相分别独立存在，并没有在制备过程中与NiO或Fe 2O 3高温下形成新的物相结构。
2.SEM测试。将实施例1-4和对比实施例1制备的氧载体进行，测试结果如图2-5所示。三种改性剂掺杂后的氧载体明显分散性更好，具有更丰富的孔隙结构。
应用实施例
1.第一组应用实施例。将氧载体在固定床管式反应器中，先后通入生物油制备合成气，然后通过水蒸汽制备氢气，具体如下所述。
应用实施例1.1 Ni15Fe60Ce25复合氧载体
(1)称取10g载氧体放入固定床管式反应器，在空气氛围下升温至900℃，然后再用氮气吹托10min,排净管内空气后，利用注射泵共通入为2.8ml、流速为0.14ml/min的生物油和3.36ml、流速为0.168ml/min的水蒸气；同时利用在线色谱分析尾气组分含量及产率；
(2)待色谱中各气体组分浓度降至0.5％以下，通入10ml,流速为0.165ml/min的去离子水，利用在线色谱分析氢气浓度及产量。
其中，载气流速(空气，氮气)均为500ml/min；色谱对尾气组分记录时间间隔单位为秒，其中尾气各组分含量以500ml/min氮气为基准计算。
应用实施例1.2 Ni15Fe60Zr25复合氧载体。
应用实施例1.3 Ni15Fe60Al25复合氧载体。
应用实施例1.4 Ni20Fe80复合氧载体。
2.第二组应用实施例。本应用实施例与第一组实施例不同之处在于，将复合氧载体进行了5次循环测试，具体如下所述。
应用实施例2.1 Ni15Fe60Ce25复合氧载体
(1)称取10g载氧体放入固定床管式反应器，在空气氛围下升温至900℃，然后再用氮气吹托10min,排净管内空气后，利用注射泵共通入为 2.8ml、流速为0.14ml/min的生物油和3.36ml、流速为0.168ml/min的水蒸气；同时利用在线色谱分析尾气组分含量及产率；
(2)待色谱中各气体组分浓度降至0.5％以下，通入10ml,流速为0.165ml/min的去离子水，利用在线色谱分析氢气浓度及产量。
(3)再通入空气，待色谱中氧气组分达到21％左右，即说明氧载体得到完全氧化再生；然后继续重复(1)(2)(3)，达到5次为止。
其中，载气流速(空气，氮气)均为500ml/min；色谱对尾气组分记录时间间隔单位为秒，其中尾气各组分含量以500ml/min氮气为基准计算。
应用实施例2.2 Ni15Fe60Zr25复合氧载体。
应用实施例2.3 Ni15Fe60Al25复合氧载体。
应用实施例2.4 Ni20Fe80复合氧载体。
将应用实施例1.1-1.4进行合成气产率测试，测试结果如图6所示。从图6中可以看到Ni15Fe60Ce25氧载体相较于Ni20Fe80，合成气产率从1.77Nm 3/kg提升至2.01Nm 3/kg，合成气纯度从78.9％提升到81％左右，同时H 2/CO比从1.98提升至2。这种积极的变化是由于CeO 2不仅具有很强的氧迁移速率，同时对合成气也有着更高的选择性。而Ni15Fe60Zr25氧载体的合成气产率略有提升，但H 2/CO却出现明显下跌，这是因为ZrO 2属于一种惰性载体，不直接参与反应。
将应用实施例1.1-1.4进行氢气纯度测试，测试结果如图7所示。从图7中可知Ni15Fe60Ce25改性氧载体氢气的纯度及产率相较于Ni20Fe80氧载体进一步得到提升。这是因为Fe 2O 3与CeO 2之间同样存在积极的协同作用，即使是简单的物理接触也能提高Fe 2O 3的还原性；此外Fe-Ce固溶体的形成以及钙钛矿型CeFeO3的出现都会极大地促进氧空位的产生，加快晶格氧从氧载体内部向表面迁移。而Ni15Fe60Zr25氧载体在氢气纯度及产率方面出现了下跌，这可能是惰性载体ZrO 2的加入，减少了活性组分NiFe 2O 4的含量，降低了对Fe 2O 3的还原引起的。最后通过对Ni15Fe60Al25氧载体制氢 能力的观察，我们发现其氢气产率及纯度异常的低，这是因为在反应过程中有惰性尖晶石FeAl 2O 4的形成，而这种结构不利于Fe元素的进一步还原和氧化。
将应用实施例1.1-1.4生物油还原阶段物相结构进行XRD测试，测试结果如图8所示。还原态的Ni15Fe60Ce25氧载体出现了钙钛矿型结构CeFeO 3，Ni15Fe60Ce25氧载体相比Ni20Fe80氧载体的氢气产率及合成气的产率均有提升与这种结构的出现有关。
Ni15Fe60Zr25氧载体经过生物油还原后出现了大量Fe 3O 4的结构，这可能是由于惰性载体ZrO 2的加入,导致氧载体内部NiFe 2O 4减少,从而变相提高了Fe 2O 3的还原难度。但是可以看到ZrO 2在反应阶段没有发生变化，也证明了其自身热稳定性非常好。
针对Ni15Fe60Al25氧载体，在还原阶段的确发现了惰性尖晶石FeAl 2O 4的出现，但还发现了另一种尖晶石AlFe 2O 4的形成。AlFe 2O 4属于高温物相，即860℃以上才能存在，是由Fe 3O 4与FeAl 2O 4高温下互溶形成的。FeAl 2O 4稳定性很强，且由于热力学限制，在1123K以下，FeAl 2O 4几乎不与水蒸气反应，同时AlFe 2O 4的形成也会大大降低氧化还原反应的热力学驱动力，因此制氢能力明显降低。
将应用实施例2.1-2.4进行5次循环的合成气产率测试，测试结果如图9所示。从图9可知，Ni15Fe60Ce25氧载体在5次循环中合成气的产率在，合成气纯度维持在81％左右；Ni15Fe60Zr25氧载体的合成气产率在，合成气纯度随循环次数增加略有提升。但是Ni15Fe60Ce25与Ni15Fe60Zr25两种改性后的氧载体在多次循环中相比Ni20Fe80有更高的合成气纯度及产率。而Ni15Fe60Al25氧载体合成气的产率及纯度随循环次数增加而不断上涨，根据研究可以推测这可能是由于在多次循环过程中惰性尖晶石FeAl 2O 4与固溶体AlFe 2O 4不断增加，导致氧载体晶格氧释放严重受阻，其合成气产率及纯度的提高则是FR反应器中越来越多的积碳与水蒸气发生反应所引起。
将应用实施例2.1-2.4进行氢气纯度测试，测试结果如图10所示。由图10可知，Ni15Fe60Ce25在5次循环制氢过程中，不仅氢气产率最高并且氢气纯度一直维持在96％左右，制备氢与合成气的性能得到进一步的提升，同时表现出了优异的循环稳定性。而这则表明了CeO 2的掺杂，以及钙钛矿CeFeO 3的形成保证了氧载体的循环稳定性。
Ni15Fe60Zr25同样在5次循环过程中表现出了优异的循环稳定性，这是因为ZrO2具有更强的结构稳定性，能够在多次循环保证氧载体孔隙结构不发生明显变化，从而保证晶格氧的释放速率稳定。但是Ni15Fe60Zr25氢气产率及纯度则相对较低，这是因为ZrO 2不参与反应，而NiFe 2O 4结构随Fe 2O 3相对质量分数减少而减少，从而降低了氧载体中Fe的还原性。
同样的，Ni15Fe60Al25氧载体制氢能力明显降低是因为两种惰性尖晶石结构FeAl 2O 4与AlFe 2O 4在反应过程中形成所引起的，这在上一节XRD的表征分析已经得到了证实。但是从第二次循环开始，Ni15Fe60Al25氧载体制氢能力再次出现明显下降，但在随后循环中氢气产率相对稳定，氢气纯度也维持在85％左右。这也从侧面表现出FeAl 2O 4与AlFe 2O 4结构的稳定性，极大缓解了Fe元素在还原过程中的烧结现象。
将应用实施例2.1-2.4 5次循环后的复合氧载体进行XRD测试，测试结果如图11所示。Ni20Fe80氧载体中的NiFe2O4结构出现了明显的相分离，而Ni15Fe60Ce25,Ni15Fe60ZrO2,Ni15Fe60Al25三种改性氧载体中NiFe2O4的结晶度仍很高，说明改性金属的添加保证了氧载体结构的稳定。但是Ni15Fe60Al25依旧有FeAl2O4的物相结构，这对于产氢来讲是不利的。因此，结合上述讨论分析可得Ni15Fe60Ce25是最佳的改性氧载体。
将应用实施例2.1-2.4 5次循环后的复合氧载体进行SEM测试，测试结果如图12-15所示。Ni20Fe80氧载体出现了明显的孔隙结构坍塌，表面团聚现象明显，而Ni15Fe60Ce25,Ni15Fe60ZrO2,Ni15Fe60Al25三种改性氧载体的结构依旧稳定，这说明了三种改性金属的添加对氧载体的循环稳定 性起到了积极的作用。其中Ni15Fe60Ce25氧载体的孔隙结构更为明显，这对于晶格氧的释放是有利的，同时也证明了上述相关测试结果。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种改性镍铁复合氧载体的制备方法，其特征在于，将氧化镍，三氧化二铁和改性剂加水混合均匀后干燥得到前驱体，将前驱体在900-1000℃煅烧6-9h，即可获得改性镍铁复合氧载体；所述改性剂为氧化铈、氧化铝、氧化锆中的一种或多种的混合。
  2. 根据权利要求1所述的制备方法，其特征在于，所述改性剂为氧化铈。
  3. 根据权利要求1所述的制备方法，其特征在于，所述氧化镍、三氧化二铁和改性剂的质量之比为(15-25)：(50-60)：(15-25),优选的，所述氧化镍与所述三氧化二铁的质量比为1:4。
  4. 根据权利要求2或3所述的制备方法，其特征在于，步骤(1)中所述干燥为恒温干燥，所述恒温干燥的温度为100-120℃，干燥时间为6-9h。
  5. 根据权利要求1所述的制备方法，其特征在于，所述氧化镍，所述三氧化二铁和所述改性剂是通过球磨混合均匀。
  6. 一种改性镍铁复合氧载体，其特征在于，根据权利要求1-5任一项所述的制备方法制备而成。
  7. 根据权利要求6所述的改性镍铁复合氧载体的应用，其特征在于，所述应用为基于化学链技术耦合制氢与合成气的应用。
  8. 根据权利要求7所述的镍铁复合氧载体的应用，其特征在于，所述基于化学链技术耦合制氢与合成气的应用包括以下步骤：
    (1)将改性镍铁复合氧载体与生物油混合后反应，获得还原态的改性镍铁复合氧载体和合成气；
    (2)将还原态的改性镍铁复合氧载体与水蒸气反应，获得氢气，还原态的改性镍铁复合氧载体得到部分氧化；
    (3)部分氧化后的改性镍铁复合氧载体通过空气彻底氧化，完成再生。
  9. 根据权利要求8所述的改性镍铁复合氧载体的应用，其特征在于，所述步骤(1)中还加入了水蒸气，所述水蒸汽的液体体积与生物油的液体体积之比值为1.2-2。
  10. 根据权利要求9所述的改性镍铁复合氧载体的应用，其特征在于，所述步骤(1)，步骤(2)和步骤(3)的反应温度为900℃，所述生物油为有机固废热解而成，所述合成气为CO和H 2的混合气体。
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