WO2022141978A1 - 一种镍掺杂钙铁石型氧载体及其制备方法和应用 - Google Patents

一种镍掺杂钙铁石型氧载体及其制备方法和应用 Download PDF

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WO2022141978A1
WO2022141978A1 PCT/CN2021/089625 CN2021089625W WO2022141978A1 WO 2022141978 A1 WO2022141978 A1 WO 2022141978A1 CN 2021089625 W CN2021089625 W CN 2021089625W WO 2022141978 A1 WO2022141978 A1 WO 2022141978A1
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nickel
oxygen carrier
doped
type oxygen
mol
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许婷婷
王训
肖波
蒋聪
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • 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
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/061—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water with metal oxides
    • C01B3/063—Cyclic methods
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention belongs to the technical field of chemical chain combustion oxygen carriers, and in particular relates to a nickel-doped mayorite type oxygen carrier and a preparation method and application thereof.
  • Hydrogen is an ideal clean energy with high energy density, and the development of a hydrogen energy economy can reduce the emission of greenhouse gases and fine particulate matter.
  • countries and regions around the world regard hydrogen energy as the strategic development direction of new energy in the future, and actively build a hydrogen energy low-carbon society.
  • my country is the largest hydrogen producing country in the world, and its industrial hydrogen production leads the world.
  • Coal-to-hydrogen is one of the main hydrogen production technologies in my country.
  • coal-based hydrogen production technology has disadvantages such as complex equipment structure, relatively low operation cycle, high desulfurization investment, many supporting devices, serious carbon emissions, and high hydrogen production cost. Therefore, the development of new hydrogen production technology is of great significance to the development of hydrogen energy economy in my country.
  • the chemical chain reforming technology utilizes the lattice oxygen in the oxygen carrier (MexOy) to partially oxidize the fuel, and regulates the ratio of H2 and CO by controlling the ratio of the oxygen carrier to the fuel.
  • the target product of chemical chain reforming is syngas, but it still needs further conversion and separation to obtain high-concentration hydrogen.
  • the complete combustion of lattice oxygen and fuel produces CO 2 and H 2 O.
  • the oxygen carrier reacts with water in a steam reactor to produce H 2 , and finally high-purity hydrogen can be produced by condensation. It also captures CO 2 .
  • Combining chemical chain reforming and chemical chain hydrogen production technology can realize the co-production of high-concentration hydrogen and synthesis gas in one process, that is, chemical chain co-production of hydrogen and synthesis gas.
  • This process integrates many advantages of chemical chain reforming and chemical chain hydrogen production technology, greatly improves the energy utilization efficiency, and can obtain relatively pure synthesis gas and high concentration hydrogen (purity of more than 98%), which is extremely developed. potential.
  • perovskite oxygen carriers can realize the co-production of hydrogen and syngas without the need for an air reactor, however, perovskite oxygen carriers face problems such as Fe 3 C formation, Problems such as carbon deposition, weak oxygen release ability, and easy sintering need to be optimized and improved, and nickel-doped mayorite-type oxygen carrier has become an important improvement route.
  • CN101802495A discloses a method and equipment for burning carbonaceous fuel using a solid oxygen carrier, and specifically discloses introducing a particulate oxygen selective sorbent into an adsorption reactor of the combustion equipment to form first particles in the adsorption reactor bed, and then burn the fuel through an oxygen-selective sorbent, the oxygen-selective sorbent of the technical solution comprises mayorite oxide, and is modified with a substance that promotes the oxygen adsorption performance of the material, and the accelerator substance is selected from Cu, Ag, Fe, Ni, Rh, Pt or mixtures of these.
  • the technical solution discloses a nickel-doped mayorite-type oxygen carrier, it does not give its preparation method, nor its application in the field of chemical chain combustion.
  • the prior art still lacks a method for preparing a nickel-doped mayorite-type oxygen carrier that can be used for chemical chain combustion.
  • the present invention provides a method for preparing a nickel-doped mayorite-type oxygen carrier.
  • the CH decoupling ability of nickel oxide is used.
  • the unique advantages of Ca 2 Fe 2 O 5 in hydrogen production the chemical chain reforming synthesis gas technology and the chemical chain hydrogen production technology are coupled to achieve high-quality synthesis gas and pure hydrogen in one process. Therefore, the problems of low activity of the oxygen carrier of Ca 2 Fe 2 O 5 , low carbon conversion efficiency and poor stability are solved.
  • the detailed technical solutions of the present invention are as follows.
  • a method for preparing a nickel-doped mayorite-type oxygen carrier wherein calcium salt, nickel salt, iron salt and organic acid are dissolved in water and mixed uniformly to obtain a precursor; After the precursor is dried, it is calcined at 900-1200 °C for 10 h to obtain a nickel-doped mayorite-type oxygen carrier.
  • the calcium salt is one of calcium nitrate, calcium chloride and calcium dihydrogen phosphate
  • the nickel salt is one of nickel nitrate, nickel chloride and nickel dihydrogen phosphate
  • the iron salt is A kind of ferric nitrate, ferric chloride and ferric dihydrogen phosphate
  • the organic acid is a kind of citric acid, tartaric acid and malic acid.
  • the uniform mixing is to stir the mixture of calcium salt, nickel salt, iron salt and organic acid in an oil bath heating environment, the oil bath temperature is 80-100 ° C, the stirring time is 6-10 h, and the drying Is at 100-120 °C, drying 12-24h.
  • a nickel-doped mayorite-type oxygen carrier which is prepared according to the aforementioned preparation method.
  • an application of a nickel-doped mayorite type oxygen carrier is the application of coupling production of high-purity hydrogen and synthesis gas based on chemical chain technology, and the synthesis gas is a mixture of carbon monoxide and hydrogen Gas, the high-purity hydrogen refers to hydrogen with a purity of more than 96%.
  • the reduced oxygen carrier reacts with water vapor to obtain hydrogen, and the reduced oxygen carrier is regenerated into a nickel-doped mayorite type oxygen carrier.
  • the step (1) is carried out in a reforming reactor
  • the step (2) is carried out in a steam reactor, and both the reforming reactor and the steam reactor adopt a fluidized bed reactor.
  • water vapor is also added in the step (1), and the molar ratio (S/C) of the water vapor to the carbon in the bio-oil is 0.1-0.5.
  • the reaction temperature is 800-1000°C.
  • the lattice distortion caused by Ni-doping causes a phase transition after the doping of mayorite, which is helpful to promote the release of lattice oxygen and increase the lattice Oxygen release rate, improving the characteristic of low redox activity of mayorite, improving carbon conversion rate and hydrogen production capacity in the water vapor oxidation stage.
  • the nickel-doped mightierite type oxygen carrier of the present invention has the advantages of high activity, strong target product selectivity, outstanding hydrogen production capacity, etc., and realizes the co-production of bio-oil chemical chain hydrogen and synthesis gas; through optimization of process parameters, The bio-oil can be reformed into high-quality syngas with high efficiency, and the carbon conversion rate can reach 97.20%; the purity of hydrogen in the steam oxidation stage can also be as high as 98%, which fully meets the requirements of industrial application.
  • the method for co-preparing hydrogen and synthesis gas by nickel-doped mayorite type oxygen carrier of the present invention overcomes the application defect of bio-oil in chemical chain technology, and can promote the higher value of bio-oil It is more economical, more practical, and has broader application prospects.
  • Fig. 1 is a schematic diagram of the co-production of hydrogen and synthesis gas by using the nickel-doped mayorite-type oxygen carrier of the present invention.
  • FIG. 2 is an XRD test chart of the oxygen carrier prepared in Comparative Example 1.
  • FIG. 2 is an XRD test chart of the oxygen carrier prepared in Comparative Example 1.
  • FIG. 3 is an XRD test chart of the oxygen carrier prepared in Example 1.
  • FIG. 4 is an XRD test chart of the oxygen carrier prepared in Example 2.
  • FIG. 5 is an XRD test chart of the oxygen carrier prepared in Example 3.
  • FIG. 5 is an XRD test chart of the oxygen carrier prepared in Example 3.
  • FIG. 6 is an XRD test chart of the oxygen carrier prepared in Example 4.
  • FIG. 6 is an XRD test chart of the oxygen carrier prepared in Example 4.
  • a nickel-doped mayorite-type oxygen carrier is prepared by the following method:
  • a nickel-doped mayorite-type oxygen carrier is prepared by the following method:
  • a nickel-doped mayorite-type oxygen carrier is prepared by the following method:
  • a nickel-doped mayorite-type oxygen carrier is prepared by the following method:
  • FIG. 2 is the XRD test chart of the oxygen carrier prepared in Comparative Example 1.
  • FIG. 3 is an XRD test chart of the oxygen carrier prepared in Example 1.
  • FIG. 4 is an XRD test chart of the oxygen carrier prepared in Example 2.
  • FIG. 5 is an XRD test chart of the oxygen carrier prepared in Example 3.
  • FIG. 6 is an XRD test chart of the oxygen carrier prepared in Example 4.
  • the undoped oxygen carrier is mainly composed of Ca 2 Fe 2 O 5.
  • the Ni-doped oxygen carrier is mainly composed of NiO, Ni 0.6 It consists of Fe 2.4 O 4 and Ca 2 Fe 2 O 5 .
  • FIG. 1 A schematic diagram of co-preparation of hydrogen and synthesis gas by using the nickel-doped mayorite-type oxygen carrier of the present invention is shown in FIG. 1 .
  • the first set of application examples In a fixed-bed tubular reactor, the oxygen carrier is successively passed into the bio-oil simulant toluene to prepare synthesis gas, and then steam is used to prepare hydrogen, as described below.
  • the Ca 2 Fe 1.75 Ni 0.25 O 5 oxygen carrier was placed in a fluidized bed reactor, and the temperature was raised to 900° C. in an air atmosphere, and then the reactor was purged with nitrogen to remove the air in the tube.
  • Syngas purity is the sum of the CO and H2 concentrations in the product gas.
  • the difference between this application example and application example 1.1 is that the oxygen carrier is different, and the oxygen carrier is Ca 2 Fe 1.50 Ni 0.50 O 5 .
  • the difference between this application example and application example 1.1 is that the oxygen carrier is different, and the oxygen carrier is Ca 2 Fe 1.25 Ni 0.75 O 5 .
  • the difference between this application example and application example 1.1 is that the oxygen carrier is different, and the oxygen carrier is Ca 2 Fe 1.00 Ni 1.00 O 5 .
  • the difference between this application example and application example 1.1 is that the oxygen carrier is different, and the oxygen carrier is Ca 2 Fe 2 O 5 .
  • reaction temperature is different. Specifically, Ca 2 Fe 1.50 Ni 0.50 O 5 is used as the oxygen carrier, and the reaction is carried out at different reaction temperatures, as described below.
  • the third group of application examples The difference between this application example and the first group of application examples is that Ca 2 Fe 1.50 Ni 0.50 O 5 is used as the oxygen carrier, and water vapor is introduced in step (2), as described below.
  • Table 1 is the test result table of the first group of application examples
  • Table 2 is the test result table of the second group of application examples
  • Table 3 is the test result table of the third group of application examples.
  • the reaction temperature is 900 °C and the water-carbon ratio is 0.28
  • the Ca 2 Fe 1.50 Ni 0.50 O 5 oxygen carrier has a better effect in the chemical chain coupling of hydrogen production and synthesis gas, and the hydrogen purity is more than 98%. , to meet the requirements of industrial applications, and at the same time to prepare syngas.

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Abstract

本发明属于化学链燃烧氧载体技术领域，具体涉及一种镍掺杂钙铁石型氧载体及其制备方法和应用。本发明制备方法包括将钙盐、镍盐、铁盐和有机酸加水溶解后混合均匀获得前驱体，将前驱体干燥后，在900-1200℃煅烧10h,即可获得镍掺杂钙铁石型氧载体。本发明的镍掺杂钙铁石型氧载体共制备氢与合成气方法与现有的化学链技术相比，克服了生物油在化学链技术中应用缺陷，能够促进生物油更加高值化利用，得到更丰富的能源产品；经济性更好，实用性更强，具有更广阔的应用前景。

Description

一种镍掺杂钙铁石型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，具体涉及一种镍掺杂钙铁石型氧载体及其制备方法和应用。
【背景技术】
氢是一种能量密度高的理想清洁能源，发展氢能经济能够减少温室气体和细颗粒物的排放。全球各国家地区纷纷将氢能源视为未来新能源的战略发展方向，积极构建氢能低碳社会。我国是世界最大的制氢国，工业氢气产量领跑全球，煤制氢是我国主要的制氢技术之一。但煤制氢技术存在设备结构复杂、运转周期相对低、脱硫投资高、配套装置多、碳排放严重、制氢成本过高等缺点。因此，开发新型的制氢技术对我国发展氢能经济具有重大意义。
近年来，基于化学链燃烧技术原理，研究人员开发了一系列制氢技术，如化学链重整、化学链制氢技术。化学链重整技术是利用氧载体(MexOy)中的晶格氧将燃料部分氧化，通过控制氧载体与燃料的比例来调控H 2和CO的比例。化学链重整目标产物是合成气，但仍需要进一步转换、分离才能获得高浓度氢气。而在化学链制氢技术中，晶格氧与燃料完全燃烧产生CO 2和H 2O，还原后氧载体在水蒸汽反应器中与水反应制取H 2，最终通过冷凝即可制备高纯氢，同时还能捕捕获CO 2。
将化学链重整以及化学链制氢技术相结合，可在一个流程中实现了高浓度氢气与合成气的共制备，也即是化学链共制氢与合成气工艺。该工艺综合了化学链重整以及化学链制氢技术的诸多优点，极大的提高了能源利用效率，并能得到较为纯净的合成气与高浓度氢气(纯度达98％以上)，极具发展潜力。
选择合适的氧载体对于实现上述化学链共制氢与合成气极其关键。研究表明钙铁石(Ca 2Fe 2O 5)氧载体可在不需要空气反应器的条件下实现氢与合成气的共制备，但是，钙钛矿氧载体该工艺中面临诸如Fe 3C形成、碳沉积、释氧能力弱、易烧结等问题，需要对其进行优化改进，而镍掺杂钙铁石型氧载体成为重要的改进路线。
CN101802495A公开了使用固体氧载体来燃烧碳质燃料的方法和设备，具体公开了将颗粒状氧气选择性吸着剂引入到该燃烧设备的吸附反应器中，来在该吸附反应器中形成第一颗粒床，进而通过氧气选择性吸着剂燃烧燃料，该技术方案的氧气选择性吸着剂包含钙铁石氧化物，并且用促进所述材料的氧气吸附性能的物质进行改性，促进剂物质选自Cu、Ag、Fe、Ni、Rh、Pt或者这些的混合物。虽然该技术方案公开了一种镍掺杂钙铁石型氧载体，但并没有给出其制备方法，也没有给出其在化学链燃烧领域的应用。
综上所述，现有技术仍缺乏能够使用于化学链燃烧的镍掺杂钙铁石型氧载体的制备方法。
【发明内容】
针对现有技术的以上缺陷，本发明了提供了一种镍掺杂钙铁石型氧载体的制备方法，通过将Ni掺杂进入到Ca 2Fe 2O 5中，借助氧化镍的C-H解耦能力，以及Ca 2Fe 2O 5在制氢方面的独特优势，将化学链重整制合成气技术与化学链制氢技术耦合，实现在一个流程内同时获取高品质的合成气以及纯净的氢气，由此解决Ca 2Fe 2O 5氧载体活性低、碳转化效率低、稳定性差等问题。本发明详细技术方案如下所述。
为实现上述目的，按照本发明的一个方面，提供了一种镍掺杂钙铁石型氧载体的制备方法，将钙盐、镍盐、铁盐和有机酸加水溶解后混合均匀获得前驱体，将前驱体干燥后，在900-1200℃煅烧10h,即可获得镍掺杂钙铁石型氧载体。
作为优选，所述镍盐的物质的量Mol Ni、所述铁盐物质的量Mol Fe与所述 钙盐的物质的量Mol Ca，满足下列关系式：(Mol Ni+Mol Fe)：Mol Ca＝1:1，Mol Ni：Mol Fe＝(1-2)：(1-0.5)。
作为优选，所述有机酸的物质的量Mol acid，满足下列关系式：(Mol Ni+Mol Fe+Mol Ca)：Mol acid＝1:(2-4)。
作为优选，所述钙盐为硝酸钙、氯化钙和磷酸二氢钙中的一种，所述镍盐为硝酸镍、氯化镍和磷酸二氢镍中的一种，所述铁盐为硝酸铁、氯化铁和磷酸二氢铁中的一种，所述有机酸为柠檬酸、酒石酸和苹果酸中的一种。
作为优选，所述混合均匀是将钙盐、镍盐、铁盐和有机酸的混合物在油浴加热环境下进行搅拌，油浴温度为80-100℃，搅拌时间为6-10h，所述干燥是在100-120℃，干燥12-24h。
按照本发明的另一个方面，提供了一种镍掺杂钙铁石型氧载体，根据前面所述的制备方法制备而成。
按照本发明的另一个方面，提供了一种镍掺杂钙铁石型氧载体的应用，所述应用为基于化学链技术耦合制高纯氢与合成气的应用，所述合成气为一氧化碳和氢气的混合气体，所述高纯氢指的是纯度为96％以上的氢气。
作为优选，包括以下步骤：
(1)将镍掺杂钙铁石型氧载体与生物油混合，获得还原态氧载体和合成气；
(2)还原态氧载体与水蒸气反应，获得氢气，还原态氧载体再生为镍掺杂钙铁石型氧载体。
作为优选，所述步骤(1)在重整反应器中进行，所述步骤(2)在蒸汽反应器中进行，所述重整反应器和所述蒸汽反应器均采用流化床反应器。
作为优选，所述步骤(1)中还加入了水蒸气，所述水蒸气与生物油中炭的摩尔比(S/C)为0.1-0.5，所述步骤(1)和步骤(2)的反应温度为800-1000℃。
本发明的有益效果有：
(1)本发明制备出的镍掺杂钙铁石型氧载体，Ni掺杂引起的晶格畸变，使得钙铁石掺杂后产生了相变，有助于促进晶格氧的释放，增加晶格氧的释放速率，改善钙铁石氧化还原活性较低的特点，提高碳转化率以及水蒸气氧化阶段的产氢能力。
(2)本发明镍掺杂钙铁石型氧载体具有活性高，目标产物选择性强，制氢能力突出等优势，实现了生物油化学链氢与合成气的共制备；通过工艺参数的优化，可高效率将生物油重整为高品质合成气，碳转化率可达97.20％；在蒸汽氧化阶段氢气的纯度也可高达98％，完全满足工业化应用要求。
(3)本发明的镍掺杂钙铁石型氧载体共制备氢与合成气方法与现有的化学链技术相比，克服了生物油在化学链技术中应用缺陷，能够促进生物油更加高值化利用，得到更丰富的能源产品；经济性更好，实用性更强，具有更广阔的应用前景。
【附图说明】
图1是应用本发明镍掺杂钙铁石型氧载体共制备氢与合成气示意图。
图2是对比实施例1制备的氧载体的XRD测试图。
图3是实施例1制备的氧载体的XRD测试图。
图4是实施例2制备的氧载体的XRD测试图。
图5是实施例3制备的氧载体的XRD测试图。
图6是实施例4制备的氧载体的XRD测试图。
【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
一种镍掺杂钙铁石型氧载体，通过以下方法制备而成：
称取0.20mol的硝酸钙Ca(NO 3) 2，0.175mol的硝酸铁Fe(NO 3) 3，0.025mol硝酸镍Ni(NO 3) 2,1.20mol的柠檬酸置于烧杯中，向烧杯中加入1000ml去离子水，将烧杯转移至95℃油浴锅中加热搅拌8h获得前驱体。将前驱体在105℃的恒温干燥箱内，干燥12h，然后放入马弗炉内，在1000℃下煅烧10h，即可获得镍掺杂钙铁石型氧载体,记为Ca 2Fe 1.75Ni 0.25O 5氧载体。
实施例2
一种镍掺杂钙铁石型氧载体，通过以下方法制备而成：
称取0.20mol的硝酸钙Ca(NO 3) 2，0.150mol的硝酸铁Fe(NO 3) 3，0.050mol硝酸镍Ni(NO 3) 2,1.20mol的柠檬酸置于烧杯中，向烧杯中加入1000ml去离子水，将烧杯转移至95℃油浴锅中加热搅拌8h获得前驱体。将前驱体在105℃的恒温干燥箱内，干燥12h，然后放入马弗炉内，在1000℃下煅烧10h，即可获得镍掺杂钙铁石型氧载体,记为Ca 2Fe 1.50Ni 0.50O 5氧载体。
实施例3
一种镍掺杂钙铁石型氧载体，通过以下方法制备而成：
称取0.2mol的硝酸钙Ca(NO 3) 2，0.125mol的硝酸铁Fe(NO 3) 3，0.075mol硝酸镍Ni(NO 3) 2,1.20mol的柠檬酸置于烧杯中，向烧杯中加入1000ml去离子水，将烧杯转移至95℃油浴锅中加热搅拌8h获得前驱体。将前驱体在105℃的恒温干燥箱内，干燥12h，然后放入马弗炉内，在1000℃下煅烧10h，即可获得镍掺杂钙铁石型氧载体,记为Ca 2Fe 1.25Ni 0.75O 5氧载体。
实施例4
一种镍掺杂钙铁石型氧载体，通过以下方法制备而成：
称取0.20mol的硝酸钙Ca(NO 3) 2，0.100mol的硝酸铁Fe(NO 3) 3，0.100mol 硝酸镍Ni(NO 3) 2,1.20mol的柠檬酸置于烧杯中，向烧杯中加入1000ml去离子水，将烧杯转移至95℃油浴锅中加热搅拌8h获得前驱体。将前驱体在105℃的恒温干燥箱内，干燥12h，然后放入马弗炉内，在1000℃下煅烧10h，即可获得镍掺杂钙铁石型氧载体,记为Ca 2Fe 1.00Ni 1.00O 5氧载体。
对比实施例1
称取0.20mol的硝酸钙Ca(NO 3) 2，0.20mol的硝酸铁Fe(NO 3) 3，1.20mol的柠檬酸置于烧杯中，向烧杯中加入1000ml去离子水，将烧杯转移至95℃油浴锅中加热搅拌8h获得前驱体。将前驱体在105℃的恒温干燥箱内，干燥12h，将所得凝胶放入马弗炉内，1000℃下煅烧10h，即可获得钙铁石型氧载体,记为Ca 2Fe 2O 5氧载体。
测试实施例
XRD测试。将实施例1-4和对比实施例1制备的氧载体进行XRD测试，测试结果如图2-6所示。其中，图2是对比实施例1制备的氧载体的XRD测试图。图3是实施例1制备的氧载体的XRD测试图。图4是实施例2制备的氧载体的XRD测试图。图5是实施例3制备的氧载体的XRD测试图。图6是实施例4制备的氧载体的XRD测试图。
从图2可以看出，未掺杂的氧载体主要由Ca 2Fe 2O 5构成，采用Ni掺杂后，由图3-6可以看出，Ni掺杂的氧载体主要由NiO、Ni 0.6Fe 2.4O 4、Ca 2Fe 2O 5构成。
应用实施例
应用本发明镍掺杂钙铁石型氧载体共制备氢与合成气示意图，如图1所示。
1.第一组应用实施例。将氧载体在固定床管式反应器中，先后通入生物油模拟物甲苯制备合成气，然后通过水蒸汽制备氢气，具体如下所述。
应用实施例1.1
(1)将Ca 2Fe 1.75Ni 0.25O 5氧载体放置于流化床反应器，在空气氛围下升温 至900℃，然后再用氮气吹扫反应器,排净管内空气。
(2)注入甲苯制取合成气，利用在线气体分析仪测定产气中组分含量，待在线气体分析仪中各气体组分浓度降至0.5％以下视为反应结束。合成气纯度为产气中CO与H 2浓度之和。
(3)通入水蒸气制取高浓度氢气,利用在线气体分析仪测定氢气浓度，待在线气体分析仪中各气体组分浓度降至0.5％以下视为反应结束。氢气纯度为产气中氢气浓度。
应用实施例1.2
本应用实施例与应用实施例1.1不同之处在于，氧载体不同，氧载体为Ca 2Fe 1.50Ni 0.50O 5。
应用实施例1.3
本应用实施例与应用实施例1.1不同之处在于，氧载体不同，氧载体为Ca 2Fe 1.25Ni 0.75O 5。
应用实施例1.4
本应用实施例与应用实施例1.1不同之处在于，氧载体不同，氧载体为Ca 2Fe 1.00Ni 1.00O 5。
应用实施例1.5
本应用实施例与应用实施例1.1不同之处在于，氧载体不同，氧载体为Ca 2Fe 2O 5。
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，反应温度不同，具体为以Ca 2Fe 1.50Ni 0.50O 5为氧载体，在不同的反应温度下反应，具体如下所述。
应用实施例2.1反应温度为800℃。
应用实施例2.2反应温度为850℃。
应用实施例2.3反应温度为950℃。
应用实施例2.4反应温度为1000℃。
3.第三组应用实施例。本应用实施例与第一组应用实施例的区别在于，以Ca 2Fe 1.50Ni 0.50O 5为氧载体，在步骤(2)中通入了水蒸气，具体如下所述。
应用实施例3.1水蒸气与甲苯中碳的摩尔比(S/C)为0.14。
应用实施例3.2水蒸气与甲苯中碳的摩尔比(S/C)为0.28。
应用实施例3.3水蒸气与甲苯中碳的摩尔比(S/C)为0.42。
应用实施例3.4水蒸气与甲苯中碳的摩尔比(S/C)为0.56。
测试反应结束后的氢气和合成气产率，汇总后如表1、表2、表3所示。其中，表1是第一组应用实施例测试结果表，表2是第二组应用实施例测试结果表，表3是第三组应用实施例测试结果表。
表1 第一组应用实施例测试结果表
Figure PCTCN2021089625-appb-000001
表2 第二组应用实施例测试结果表
Figure PCTCN2021089625-appb-000002
表3 第二组应用实施例测试结果表
Figure PCTCN2021089625-appb-000003
结果与讨论
从表1可以看出，Ni的掺杂量越多，燃料的碳转化率越低，重整阶段气体产率越低。Ca 2Fe 2O 5掺杂Ni后合成气纯度降低，这是由于掺杂后Ni后提高了Ca 2Fe 2O 5中晶格氧的活性，导致产气中更多的还原性气体与晶格氧反应，从而降低了合成气纯度。但是，掺杂较少量的Ni时，可以显著改善氢气产率，总体上来说，掺杂Ni对氢气纯度的影响不大，综合分析认为，Ca 2Fe 1.50Ni 0.50O 5的综合性能较好，但是在应用实施例中，存在碳转化率低、合成气纯度低、氢气纯度低等缺点。
从表2可以看出，升高温度有利于提高燃料的转化率、气体产率，氢气纯度。这是由于升高温度有利于甲苯的重整，同时也增强了氧载体的反应活性，还原性气体更容易与晶格氧发生完全氧化反应，产生了较多的CO 2，导致合成气纯度较低。随着温度的升高，氢气产率降低、氢气纯度升高，这主要是由于重整阶段碳转化率升高，因此在水蒸气反应器中积碳含量降低，因此氢气产率降低但纯度升高。综合分析认为，温度为900℃时制备比较有利于氢气的制备。
从表3可以看出，适当增加水蒸气量可以显著的改善燃料碳转化率、提高气体产率、提高合成气纯度，这是由于水蒸气的加热促进了碳与水蒸气的反应及有机物的重整反应，产生更多的CO和H 2。同时，在重整反应器中加入水蒸气对于氢气产率的影响较大，氢气产率随着水蒸气的加入而递 减。在水碳比为0.28时效果最佳，过多的水蒸气会抑制氧载体在重整反应器中的还原，从而导致氢气产率的降低，水蒸气量较少则会导致重整反应器中碳转化率较低，未反应的碳在水蒸气反应器中与水反应虽然提高了氢气产率，但是氢气纯度较低。
总的来说，在反应温度为900℃，水碳比为0.28时，Ca 2Fe 1.50Ni 0.50O 5氧载体在化学链耦合制氢与合成气中的效果较好，氢气纯度达98％以上，满足工业应用要求，同时还能制备合成气。
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. 一种镍掺杂钙铁石型氧载体的制备方法，其特征在于，将钙盐、镍盐、铁盐和有机酸加水溶解后混合均匀获得前驱体，将前驱体干燥后，在900-1200℃煅烧10h,即可获得镍掺杂钙铁石型氧载体。
  2. 根据权利要求1所述的制备方法，其特征在于，所述镍盐的物质的量Mol Ni、所述铁盐物质的量Mol Fe与所述钙盐的物质的量Mol Ca，满足下列关系式：(Mol Ni+Mol Fe)：Mol Ca＝1:1，Mol Ni：Mol Fe＝(1-2)：(1-0.5)。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述有机酸的物质的量Mol acid，满足下列关系式：(Mol Ni+Mol Fe+Mol Ca)：Mol acid＝1:(2-4)。
  4. 根据权利要求3所述的制备方法，其特征在于，所述钙盐为硝酸钙、氯化钙和磷酸二氢钙中的一种，所述镍盐为硝酸镍、氯化镍和磷酸二氢镍中的一种，所述铁盐为硝酸铁、氯化铁和磷酸二氢铁中的一种，所述有机酸为柠檬酸、酒石酸和苹果酸中的一种。
  5. 根据权利要求1所述的制备方法，其特征在于，所述混合均匀是将钙盐、镍盐、铁盐和有机酸的混合物在油浴加热环境下进行搅拌，油浴温度为80-100℃，搅拌时间为6-10h，所述干燥是在100-120℃，干燥12-24h。
  6. 一种镍掺杂钙铁石型氧载体，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所述的镍掺杂钙铁石型氧载体的应用，其特征在于，所述应用为基于化学链技术耦合制高纯氢与合成气的应用，所述合成气为一氧化碳和氢气的混合气体，所述高纯氢指的是纯度为96％以上的氢气。
  8. 根据权利要求7所述的镍掺杂钙铁石型氧载体的应用，其特征在于，包括以下步骤：
    (1)将镍掺杂钙铁石型氧载体与生物油混合，获得还原态氧载体和合成气；
    (2)还原态氧载体与水蒸气反应，获得氢气，还原态氧载体再生为镍掺杂钙铁石型氧载体。
  9. 根据权利要求8所述的镍掺杂钙铁石型氧载体的应用，其特征在于，所述步骤(1)在重整反应器中进行，所述步骤(2)在蒸汽反应器中进行，所述重整反应器和所述蒸汽反应器均采用流化床反应器。
  10. 根据权利要求8或9所述的镍掺杂钙铁石型氧载体的应用，其特征在于，所述步骤(1)中还加入了水蒸气，所述水蒸气与生物油中炭的摩尔比为0.1-0.5，所述步骤(1)和步骤(2)的反应温度为800-1000℃。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116654993A (zh) * 2023-05-17 2023-08-29 南京理工大学 一种高熵氧化物氧载体及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113893859A (zh) * 2021-11-05 2022-01-07 华中科技大学 一种制备合成气的氧载体及其制备方法和两段式化学链重整焦油制备合成气的方法
CN115069256A (zh) * 2022-07-27 2022-09-20 中国科学院广州能源研究所 一种载氧体及其在纤维素类固体废弃物化学链气化中的应用
CN118289837B (zh) * 2024-04-03 2025-02-28 华中科技大学 一种钙基碳氧载体及其制备方法和在吸附增强化学链重整pet制氢中的应用
CN119701783B (zh) * 2024-12-19 2025-12-09 华中科技大学 一种低温热化学循环分解水制氢装置及制氢方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102441396A (zh) * 2010-10-12 2012-05-09 中国石油化工股份有限公司 双钙钛矿型氧化物载氧体在化学链制氢中的应用及制备方法
EP3101718A1 (en) * 2014-01-31 2016-12-07 National University Corporation Hokkaido University Catalyst for air electrode for metal/air secondary battery, and air electrode
CN107857301A (zh) * 2017-11-09 2018-03-30 东南大学 一种钙铁型Ca2Fe2O5催化剂制备方法
WO2019003079A1 (en) * 2017-06-26 2019-01-03 Rīgas Tehniskā Universitāte PHOTOCATALYTIC SYSTEM BASED ON FE 2O3 / CA2FE2O 5
CN110683511A (zh) * 2019-11-12 2020-01-14 中南大学 一种甲烷裂解制氢耦合co2还原的化学链循环方法
CN111266113A (zh) * 2020-02-27 2020-06-12 西北大学 一种用于化学链燃烧和裂解的氧载体及其制备方法和应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4281061B2 (ja) * 2004-04-15 2009-06-17 独立行政法人産業技術総合研究所 活性酸素吸蔵物質及びその製造方法
PE20140695A1 (es) * 2011-05-06 2014-06-06 Sasol Tech Pty Ltd Catalizadores
CN104900887B (zh) * 2015-06-14 2017-07-21 吉林大学 双钙钛矿型中温固体氧化物燃料电池阴极材料及制备方法
CN107537503B (zh) * 2016-06-23 2020-11-10 中国石油化工股份有限公司 一种生物质制合成气的载氧体，其制备方法及应用
CN107090323B (zh) * 2017-03-03 2019-09-17 中国科学院青岛生物能源与过程研究所 一种具有控制氧化功能的复合氧载体及其制备方法
CN106902837B (zh) * 2017-03-31 2019-07-19 天津大学 一种负载型镍钨双金属复合氧化物及其制备方法和应用
CN107804824B (zh) * 2017-11-09 2020-03-31 东南大学 一种复合型钙铁载氧体及其化学链制氢协同co2捕集方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102441396A (zh) * 2010-10-12 2012-05-09 中国石油化工股份有限公司 双钙钛矿型氧化物载氧体在化学链制氢中的应用及制备方法
EP3101718A1 (en) * 2014-01-31 2016-12-07 National University Corporation Hokkaido University Catalyst for air electrode for metal/air secondary battery, and air electrode
WO2019003079A1 (en) * 2017-06-26 2019-01-03 Rīgas Tehniskā Universitāte PHOTOCATALYTIC SYSTEM BASED ON FE 2O3 / CA2FE2O 5
CN107857301A (zh) * 2017-11-09 2018-03-30 东南大学 一种钙铁型Ca2Fe2O5催化剂制备方法
CN110683511A (zh) * 2019-11-12 2020-01-14 中南大学 一种甲烷裂解制氢耦合co2还原的化学链循环方法
CN111266113A (zh) * 2020-02-27 2020-06-12 西北大学 一种用于化学链燃烧和裂解的氧载体及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HOSSEINI DAVOOD, DONAT FELIX, ABDALA PAULA M., KIM SUNG MIN, KIERZKOWSKA AGNIESZKA M., MÜLLER CHRISTOPH R.: "Reversible Exsolution of Dopant Improves the Performance of Ca 2 Fe 2 O 5 for Chemical Looping Hydrogen Production", APPLIED MATERIALS & INTERFACES, vol. 11, no. 20, 22 May 2019 (2019-05-22), US , pages 18276 - 18284, XP055948885, ISSN: 1944-8244, DOI: 10.1021/acsami.8b16732 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116654993A (zh) * 2023-05-17 2023-08-29 南京理工大学 一种高熵氧化物氧载体及其制备方法和应用
CN116654993B (zh) * 2023-05-17 2025-09-19 南京理工大学 一种高熵氧化物氧载体及其制备方法和应用

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