WO2021000456A1 - 一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法 - Google Patents

一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法 Download PDF

Info

Publication number
WO2021000456A1
WO2021000456A1 PCT/CN2019/112056 CN2019112056W WO2021000456A1 WO 2021000456 A1 WO2021000456 A1 WO 2021000456A1 CN 2019112056 W CN2019112056 W CN 2019112056W WO 2021000456 A1 WO2021000456 A1 WO 2021000456A1
Authority
WO
WIPO (PCT)
Prior art keywords
storage alloy
carbon dioxide
hydrogen storage
reaction
room temperature
Prior art date
Application number
PCT/CN2019/112056
Other languages
English (en)
French (fr)
Inventor
欧阳柳章
刘芬
钟丹
朱敏
王辉
刘江文
曾美琴
Original Assignee
华南理工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 华南理工大学 filed Critical 华南理工大学
Publication of WO2021000456A1 publication Critical patent/WO2021000456A1/zh

Links

Images

Classifications

    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
    • C01B3/0063—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof only containing a rare earth metal and only one other metal
    • C01B3/0068—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof only containing a rare earth metal and only one other metal the other metal being nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/02—Hydrides of transition elements; Addition complexes thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
    • 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
    • Y02E60/32—Hydrogen storage

Definitions

  • the invention belongs to the technical field of clean energy, and in particular relates to a method for realizing carbon dioxide methanation at room temperature by using hydrogen storage alloy hydride.
  • the Sabatier reaction is an exothermic reaction, so low temperature thermally promotes the formation of CH 4 , which is not conducive to the formation of by-product CO; however, the reduction of fully oxidized carbon (CO 2 ) to methane has significant kinetic limitations, so catalysts are usually required It can accelerate the CO 2 kinetic conversion reaction rate at a relatively low temperature to obtain considerable methane yield and selectivity.
  • the selected catalyst needs to have good catalytic activity, selectivity and stability.
  • Ni-supported catalyst is the most noticed traditional carbon dioxide catalyst. Compared with other catalysts, Ni is low in price, and its catalytic activity and selectivity for carbon dioxide methanation reaction are excellent; but due to excessive carbon dioxide methanation process The exothermic heat of the catalyst will cause the active components of the catalyst to burn and bond surface carbon, which leads to the deactivation of the catalyst.
  • the reducing agent hydrogen used in the reaction has a wide range of sources, it is difficult to store and transport as a dangerous gas. In view of the above reasons, the use of hydrogen to achieve carbon dioxide methanation has not been widely used so far, and the controllable conversion of CO 2 under mild conditions is an important direction for future CO 2 resource utilization.
  • the purpose of the present invention is to provide a method for achieving carbon dioxide methanation at room temperature using hydrogen storage alloy hydride.
  • a method for using hydrogen storage alloy hydride to achieve carbon dioxide methanation at room temperature includes the following steps:
  • the hydrogen storage alloy hydride is placed in a ball milling tank, and then the protective atmosphere is extracted and filled with carbon dioxide-containing gas, and then a ball mill is used for ball milling reaction at room temperature to obtain methane.
  • the hydrogen storage alloy hydride is at least one of LaNi 5 H 6 , ZrNi 5 H 6 , NdNi 5 H 6 , PrNi 5 H 6 and SmNi 5 H 6 .
  • the preparation method of the hydrogen storage alloy hydride is: under a protective atmosphere, the hydrogen storage alloy is crushed and then passed through a standard sieve, and then the obtained hydrogen storage alloy is subjected to a hydrogen absorption activation reaction in a hydrogen atmosphere, and the reaction is completed and cooled to room temperature to obtain Hydrogen storage alloy hydride.
  • the hydrogen storage alloy is at least one of LaNi 5 , ZrNi 5 , NdNi 5 , PrNi 5 and SmNi 5 ; the mesh size of the standard sieve is 200-500 mesh; The pressure of the hydrogen is 1 to 4 MPa; the hydrogen absorption activation reaction is a reaction at 100 to 200° C. for 5 to 10 hours.
  • the gas containing carbon dioxide is pure CO 2 or a mixed gas containing CO 2 and a protective atmosphere;
  • the ball milling tank is a stainless steel ball milling tank, and the medium of the ball milling reaction is steel balls;
  • the mass ratio (ball-to-material ratio) of the ball milling medium and the hydrogen storage alloy hydride is 10-40:1, preferably 40:1.
  • the rotation speed of the ball mill is 300-500 revolutions per minute
  • the reaction time of the ball mill is 1-60 h, preferably 20-40 h, and more preferably 30 h.
  • the molar ratio of H 2 in the hydrogen storage alloy hydride to CO 2 gas in the ball mill tank is 1-15:1, preferably 4-12:1.
  • the protective atmosphere of the present invention is at least one of rare gas and nitrogen, preferably argon.
  • Both the room temperature and the unspecified reaction temperature in the present invention are 15-32°C.
  • the mechanism of the present invention is as follows:
  • the invention utilizes the rare earth hydrogen storage material (RNi 5 , R is rare earth element) to absorb hydrogen at room temperature to prepare hydrogen storage alloy hydride as a hydrogen donor for the carbon dioxide methanation reaction. At the same time, it can be produced in situ during the ball milling reaction.
  • Ni@R 2 O 3 catalyst in which nano-metal Ni can play a catalytic role in the methanation of carbon dioxide, and the absorption and activation effect of R 2 O 3 on CO 2 greatly improves its catalytic performance.
  • the present invention has the following advantages and beneficial effects:
  • the present invention realizes the purpose of converting carbon dioxide into clean fuel at room temperature. It produces and stores methane through the reaction of hydrogen storage alloy hydride and carbon dioxide, and provides a new method for high-density storage of methane, replacing it with hydrogen storage alloy hydride H 2 , while avoiding the insecurity of H 2 .
  • the present invention utilizes rare earth hydrogen storage material (RNi 5 ) to absorb hydrogen at room temperature to prepare hydrogen storage alloy hydride as a hydrogen donor for carbon dioxide methanation reaction.
  • RNi 5 rare earth hydrogen storage material
  • Ni@R 2 O 3 catalyst can be prepared in situ during the reaction , Can realize the reuse of waste hydrogen, follow the principles of green chemistry and atomic economy, save costs and protect the environment.
  • the Ni@R 2 O 3 catalyst generated in situ can be used as a catalyst for the methanation reaction of carbon dioxide.
  • the Ni@Ra 2 O 3 obtained has a small metal grain size (6-8 nm), and Evenly dispersed, the Ra 2 O 3 carrier has the advantage of high efficiency in absorbing and activating CO 2. Compared with traditional catalysts, it makes the ball milling reaction conditions milder and has higher catalytic activity (methane yield can reach 83.2%).
  • Ni@Ra 2 O 3 can obtain metal hydride by hydrogen absorption, so as to achieve the purpose of recycling.
  • the reaction involved in the present invention uses combustion exhaust gas carbon dioxide as a raw material to react to produce methane and water.
  • the whole reaction process is green and pollution-free, the reaction conditions are mild, the yield is high, and the by-products are small.
  • Concept of chemistry
  • the mixed gas of methane and hydrogen obtained by the reaction of hydrogen storage alloy hydride and carbon dioxide greatly overcomes the shortcomings of methane itself: that is, the introduction of hydrogen into methane can improve the rate and stability of flame combustion, reduce combustion duration and increase Thermal efficiency; it can also reduce the quenching interval of methane combustion.
  • the material preparation and transfer storage involved in the examples are all carried out under argon atmosphere; the activation reaction involved is carried out in a high temperature and high pressure reactor, and the methanation reaction is carried out in a planetary ball mill at room temperature.
  • the target gas phase product was characterized by mass spectrometry (MS) and gas chromatography, and the solid phase product was analyzed by X-ray diffractometer (XRD) or transmission electron microscope (TEM).
  • the calculation method of CO 2 conversion rate in the embodiment is:
  • CO 2 /Ar signal ratio before reaction is the ratio of signal intensity before reaction.
  • the generated gas is detected by mass spectrometry, and the signal intensity of the gas with a charge-to-mass ratio (m/z) of 15, 40, 44 is measured.
  • the product is characterized by the charge-to-mass ratio (m/z) and calculated by the signal intensity CO 2 conversion rate and CH 4 yield after the reaction. No gas products (such as CO, etc.) other than methane and H 2 were detected in mass spectrometry and gas chromatography.
  • Fig. 1 is a graph showing changes in gas phase CO 2 conversion rate and methane yield with reaction time after the ball milling reaction of LaNi 5 H 6 and CO 2 containing mixed gas (0.3 MPa) obtained in Example 1 at a speed of 500 revolutions per minute. It can be seen from the figure that as the reaction time increases, the CO 2 conversion rate and CH 4 yield first increase and then remain unchanged. The CO 2 conversion rate reaches 100% within 5 hours, and the methane yield reaches 83.2%, and the reaction reaches equilibrium within 30 hours. .
  • Example 6 is a TEM and HR-TEM characterization diagram of the obtained solid phase product after the ball milling reaction of LaNi 5 H 6 and CO 2 at 500 rotation speed/minute for 30 h obtained in Example 1. It can be seen from the figure that in the Ni@La 2 O 3 generated in situ during the ball milling reaction of LaNi 5 H 6 , Ni exists in the form of nanocrystals, and most of La 2 O 3 is in a state of incomplete crystallization. The generated Ni@La 2 O 3 makes it have high catalytic activity.
  • the gas detection method is the same as in Example 1, and no gas products (such as CO, etc.) other than methane and H 2 are detected in mass spectrometry and gas chromatography.
  • Example 2 is a graph showing changes in gas phase CO 2 conversion rate and methane yield with the ball milling speed after the LaNi 5 H 6 and CO 2 mixed gas (0.3 MPa) obtained in Example 2 were reacted at different speeds for 30 hours. It can be seen from the figure that the yield of CH 4 produced by the interaction of LaNi 5 H 6 and CO 2 at different speeds is different, and the yield of CH 4 can reach 83.2% at 500 revolutions per minute.
  • the gas detection method is the same as in Example 1, and no gas products (such as CO, etc.) other than methane and H 2 are detected in mass spectrometry and gas chromatography.
  • Fig. 3 is a graph showing changes in gas phase CO 2 conversion rate and methane yield with pressure after the LaNi 5 H 6 obtained in Example 3 reacted with CO 2 mixed gas ball milling (500 revolutions/min) at different pressures for 30 hours. It can be seen from the figure that different H 2 :CO 2 molar ratios have an effect on the reaction rate.
  • the gas detection method is the same as in Example 1, and no gas products (such as CO, etc.) other than methane and H 2 are detected in mass spectrometry and gas chromatography.
  • the gas detection method is the same as in Example 1, and no gas products (such as CO, etc.) other than methane and H 2 are detected in mass spectrometry and gas chromatography.
  • the gas detection method is the same as in Example 1, and no gas products (such as CO, etc.) other than methane and H 2 are detected in mass spectrometry and gas chromatography.
  • the gas detection method is the same as in Example 1, and no gas products (such as CO, etc.) other than methane and H 2 are detected in mass spectrometry and gas chromatography.
  • Example 3-7 LaNi 5 H 6, ZrNi 5 H 6, NdNi 5 H 6, PrNi 5 H 6, SmNi 5 H 6 and 2, respectively, a mixed gas containing CO (0.3MPa) ball mill (500 rpm /Min) After 30 hours of reaction, the obtained gas phase CO 2 conversion rate and methane yield vary with the type of hydride. It can be seen from the figure that the methane yield is highest when LaNi 5 H 6 reacts with carbon dioxide in the hydride.
  • a relatively suitable rotation speed can be selected as 500 revolutions per minute; a suitable CO 2 mixed gas pressure can be selected according to the equipment conditions to adjust the H 2 /CO 2 mole; the ball milling reaction time is 30 hours when the CH 4 yield reaches the maximum The value is the optimal ball milling reaction time; when LaNi 5 H 6 reacts with carbon dioxide in the hydride, the reaction rate is the fastest, the methane yield is the highest, and LaNi 5 H 6 is the optimal hydride.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

提供一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法。具体方法为：在保护气氛下，将储氢合金氢化物置于球磨罐中，然后抽出保护气氛，并充入含二氧化碳的气体后，在室温下采用球磨机进行球磨反应后即制得甲烷。利用储氢合金氢化物作为二氧化碳甲烷化反应供氢剂和催化剂，与现有技术相比，稀土储氢合金氢化物一方面为二氧化碳甲烷化提供H原子作为还原剂，另一方面在球磨过程中原位生成Ni@R2O3催化剂，其中纳米金属Ni对二氧化碳甲烷化起到催化作用，同时反应生成的La2O3对CO2的吸收活化作用使得其性能大大提升，最终甲烷产率可达83.2％。

Description

一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法 技术领域
本发明属于清洁能源的技术领域，具体涉及一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法。
背景技术
二氧化碳作为一种具廉价、储量丰富的C 1资源，同时也是温室气体的元凶之一，利用二氧化碳生产化学品，不仅有助于减缓二氧化碳持续大量排放所带来的全球气候变化问题，同时还开发了新的可持续合成增值化学品和燃料的途径。催化加氢是二氧化碳转化最重要的途径之一，其主要转化产物有CO，CH 4，CH 3OH，HCOOH和C 2+，这取决于反应条件和所采用的催化剂，在所有碳氢化合物中，甲烷因具有最大氢碳比(H/C)而被认为是替代燃料的潜在候选物，此外，甲烷更容易液化，并且可以通过现有的基础设施大量安全地储存，因此，二氧化碳加氢甲烷化反应(方程式(1)，Sabatier反应)是一种具有良好前景的二氧化碳转化方法。
Figure PCTCN2019112056-appb-000001
Sabatier反应是放热反应，因此低温会热促进CH 4的形成，不利于副产物CO的生成；然而，将完全氧化的碳(CO 2)还原成甲烷具有显著动力学限制，因此通常需要使用催化剂使其能在相对低的温度下加速CO 2动力学转化反应速率，才能获得可观的的甲烷产率和选择性，所选的催化剂需具备良好的催化活性、选择性以及稳定性。
Ni负载型催化剂是最受瞩目的传统型二氧化碳催化剂，与其它催化剂相比，Ni的价格低廉，且其对二氧化碳甲烷化反应催化活性和选择性都较为优异；但由于二氧化碳甲烷化过程中过多的放热会导致催化剂活性组分产生烧结合表面积碳现象，从而导致催化剂失活，此外，该反应所用的还原剂氢气虽然来源广泛，但作为危险气体其储存、运输较为困难。鉴于以上原因，目前为止利用氢气实现二氧化碳甲烷化还没得到广泛应用，而温和条件下对CO 2进行可控转化是未来CO 2资源化利用的重要方向。
发明内容
为了解决现有技术的缺点和不足之处，本发明的目的在于提供一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法。
本发明的目的通过下述方案实现：
一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法，包括以下步骤：
在保护气氛下，将储氢合金氢化物置于球磨罐中，然后抽出保护气氛，并充入含二氧化碳的气体后，在室温下采用球磨机进行球磨反应后即制得甲烷。
进一步的，所述储氢合金氢化物为LaNi 5H 6、ZrNi 5H 6、NdNi 5H 6、PrNi 5H 6和SmNi 5H 6中的至少一种。
所述储氢合金氢化物的制备方法为：在保护气氛下，将储氢合金破碎后过标准筛，然后将所得储氢合金在氢气气氛下进行吸氢活化反应，反应完成后冷却至室温得到储氢合金氢化物。
储氢合金氢化物的制备方法中，所述储氢合金为LaNi 5、ZrNi 5、NdNi 5、PrNi 5和SmNi 5中的至少一种；所述标准筛的目数为200～500目；所述氢气的压强为1～4MPa；所述吸氢活化反应为在100～200℃下反应5～10h。
进一步的，所述含二氧化碳的气体为纯CO 2或含CO 2和保护气氛的混合气体；
进一步的，所述球磨罐为不锈钢球磨罐，球磨反应的介质为钢珠；
进一步的，所述球磨介质和储氢合金氢化物的质量比(球料比)为10～40:1，优选为40:1。
进一步的，所述球磨机的转速为300～500转/分钟，球磨反应时间为1～60h，优选为20～40h，更优选为30h。
进一步的，球磨反应时，所述储氢合金氢化物中H 2与球磨罐中CO 2气体的摩尔比为1～15:1，优选为4～12:1。
进一步的，本发明所述的保护气氛为稀有气体和氮气中的至少一种，优选为氩气。
本发明所述室温和未指明反应温度均为15～32℃。
本发明的机理如下：
本发明利用稀土储氢材料(RNi 5，R为稀土元素)在室温下吸氢，制得储氢合金氢化物作为二氧化碳甲烷化反应的供氢剂，同时在进行球磨反应时，可原位生产Ni@R 2O 3催化剂，其中，纳米金属Ni对二氧化碳甲烷化可以起到催化作用，同时R 2O 3对CO 2的吸收活化作用使得其催化性能大大提升。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明实现了室温下二氧化碳转化为清洁燃料的目的，通过储氢合金氢化物和二氧化碳反应生产并存储甲烷，为甲烷的高密度存储提供了新的方法，用储氢合金氢化物代替H 2，同时避免了H 2的不安全问题。
(2)本发明利用稀土储氢材料(RNi 5)在室温下吸氢，制得储氢合金氢化物作为二氧化碳甲烷化反应供氢剂，同时反应时可原位制备Ni@R 2O 3催化剂，能够实现废氢的再利用，遵循绿色化学和原子经济的原则，节约成本，保护环境。
(3)本发明进行球磨反应时，原位生成的Ni@R 2O 3催化剂可作为二氧化碳甲烷化反应的催化剂，所得Ni@Ra 2O 3具有金属晶粒尺寸小(6-8nm)、且分散均匀，Ra 2O 3载体具有吸收活化CO 2效率高的优点，与传统催化剂对比，使得球磨反应条件更温和，具有较高的催化活性(甲烷产率可达83.2％)。同时Ni@Ra 2O 3可以通过氢化吸氢得到金属氢化物，从而达到循环利用的目的。
(4)本发明所涉及的反应以燃烧废气二氧化碳作为原料，反应生成甲烷和水，整个反应过程绿色无污染，反应条件温和，产率高，副产物少，实现了废气再利用，体现了绿色化学的理念。
(5)储氢合金氢化物与二氧化碳反应得到的甲烷与氢气的混合气体极大克服了甲烷自身的缺点：即在甲烷中引入氢气可以改善火焰燃烧的速率及稳定性，减少燃烧持续时间和提高热效率；还可以减少甲烷燃烧的淬灭间隔。
附图说明
图1为实施例1所得LaNi 5H 6与0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)分别球磨(500转/分钟)反应1h、5h、10h、15h、20h、30h、40h、60h后CO 2转化率及甲烷产率图。
图2为实施例2所得LaNi 5H 6与0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)分别在300转/分钟、400转/分钟、450转/分钟、500转/分钟 下球磨反应30h后CO 2转化率及甲烷产率图。
图3为实施例3所得LaNi 5H 6分别与0.1MPa、0.3MPa、0.6MPa、0.8MPa、1.0MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)球磨(500转/分钟)反应30h后CO 2转化率及甲烷产率图。
图4为实施例3～7所得LaNi 5H 6、ZrNi 5H 6、NdNi 5H 6、PrNi 5H 6、SmNi 5H 6分别与0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)球磨(500转/分钟)反应30h后CO 2转化率及甲烷产率图。
图5为实施例1所得LaNi 5H 6与0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)分别球磨(500转/分钟)反应1h、5h、10h、20h、30h后固体产物的XRD表征图。
图6为实施例1所得LaNi 5H 6与0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)分别球磨(500转/分钟)反应30h后所得Ni@La 2O 3的TEM(a)和HR-TEM(b)表征图。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例中涉及到材料制备以及转移存储，都是在氩气气氛的条件下所进行；所涉及的活化反应是在高温高压反应釜进行，甲烷化反应是在室温下于行星球磨罐中进行。实施例目标气相产物通过质谱(MS)和气相色谱表征，固相产物通过X射线衍射仪(XRD)或透射电镜(TEM)进行分析。
实施例中CO 2转化率计算方法为：
Figure PCTCN2019112056-appb-000002
其中“反应后CO 2/Ar信号比”为反应后气体产物在质谱分析中m/z＝44与m/z＝40两种信号强度比值，“反应前CO 2/Ar信号比”为反应前气体在质谱分析中m/z＝44与m/z＝40两种信号强度比值。
反应后甲烷的产率计算方法为：
Figure PCTCN2019112056-appb-000003
其中，“反应后CH 4/Ar信号比”为反应后气体产物在质谱分析中m/z＝15与m/z＝40两种信号强度比值，“反应前CO 2/Ar信号比”为反应前气体在质谱分析中m/z＝44与m/z＝40两种信号强度比值。
实施例1
(1)在0.1MPa氩气气氛的手套箱中，取2.5g经过电弧熔炼、充分破碎并过200目标准检验筛筛选的LaNi 5粉末装入容积为25mL高温高压反应釜(NS-25-316L)中，充入4MPa的氢气，置于150℃下反应10h，使之充分活化，然后冷却至室温，得到LaNi 5H 6；
(2)将釜内剩余气体抽出(在抽气过程中釜内气压在0.1～1MPa之间)，在氩气手套箱中，打开反应釜取出其中的氢化产物LaNi 5H 6，将其置于容积为200mL的行星球磨罐中，放入100g小钢珠(其中直径为10mm的60g，直径为6mm的40g)，将其中的氩气抽出后充入0.30MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，再次抽气、充气，反复3次后，反应釜内已无杂质气体残留，再次充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，使得氢化物中H 2/CO 2的摩尔比值为4:1，使用行星式球磨机(QM-3SP4)在500转/分钟的转速下分别球磨反应1h、5h、10h、15h、20h、30h、40h、60h，制得甲烷与氢气的混合气体。
将生成的气体通入质谱中检测，测得气体中荷质比(m/z)为15、40、44的信号强度，通过荷质比(m/z)进行产物定性，通过信号强度来计算反应后CO 2转化率及CH 4产率。在质谱和气相色谱中未测得除甲烷与H 2以外的气体产物(例如CO等)。
图1是实施例1所得LaNi 5H 6与含CO 2混合气体(0.3MPa)在500转速/分钟转速下球磨反应后，气相CO 2转化率及甲烷产率随反应时间变化图。从图中可以看出，随着反应时间增长，CO 2转化率及CH 4产率先增加后不变，CO 2转化率5小时内达到100％，甲烷产率最高为83.2％，30h反应达到平衡。
将反应后的固体产物进行XRD、SEM、TEM表征。图5为实施例1所得 LaNi 5H 6与0.3Mpa含二氧化碳的混合气体(V CO2:V Ar＝19:81)分别球磨(500转/分钟)反应1h、5h、10h、20h、30h后固体产物XRD表征图。从图5可以看出，催化反应开始后的固体有LaNi 5H 6及Ni两种物相，随着球磨时间的延长，LaNi 5H 6发生分解逐步生成Ni。图6为实施例1所得LaNi 5H 6与CO 2在500转速/分钟转速下球磨反应30h后，所得固相产物的TEM及HR-TEM表征图。从图中可以看出，LaNi 5H 6在球磨反应时原位生成的Ni@La 2O 3中，Ni以纳米晶的形态存在，La 2O 3大部分呈现晶化不完全的状态，可见生成的Ni@La 2O 3使其具有高催化活性。
实施例2
(1)在0.1MPa氩气气氛的手套箱中，取2.5g经过电弧熔炼并充分破碎，过200目标准检验筛筛选的LaNi 5粉末装入容积为25mL高温高压反应釜(NS-25-316L)中，充入4MPa的氢气，置于150℃下反应10h，使之充分活化，冷却至室温，得到LaNi 5H 6；
(2)将釜内剩余气体抽出(在抽气过程中釜内气压在0.1～1MPa之间)，在氩气手套箱中，打开反应釜取出其中的氢化产物，将其置于容积为200mL的行星球磨罐中，然后放入100g小钢珠(其中直径为10mm的60g，直径为6mm的40g)，将其中的氩气抽出后充入0.30MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，再次抽气、充气，反复3次后，反应釜内已无杂质气体残留，再次充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，使得氢化物中H 2/CO 2的摩尔比值为4:1，使用行星式球磨机(QM-3SP4)分别在300转/分钟、400转/分钟、450转/分钟、500转/分钟的转速下球磨反应30h，制得甲烷与氢气的混合气体。
气体的检测方法同实施例1，在质谱和气相色谱中未测得除甲烷与H 2以外的气体产物(例如CO等)。
图2是实施例2所得LaNi 5H 6与含CO 2混合气体(0.3MPa)分别在不同转速下反应30h后，气相CO 2转化率及甲烷产率随球磨转速变化图。从图中可以看出，不同转速下LaNi 5H 6与CO 2作用生成了CH 4的产率不同，CH 4的产率在500转/分钟下可达到83.2％。
实施例3
(1)在0.1MPa氩气气氛的手套箱中，取2.5g经过电弧熔炼并充分破碎，过200目标准检验筛筛选的LaNi 5粉末装入容积为25mL高温高压反应釜(NS-25-316L)中，充入4MPa的氢气，置于150℃下反应10h，使之充分活化，冷却至室温得到LaNi 5H 6；
(2)将釜内剩余气体抽出(在抽气过程中釜内气压在0.1～1MPa之间)，在氩气手套箱中，打开反应釜取出其中的氢化产物，将其置于容积为200mL的行星球磨罐中，放入100g小钢珠(其中直径为10mm的60g，直径为6mm的40g)，将其中的氩气抽出后充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，再次抽气、充气，反复3次后，反应釜内已无杂质气体残留，分别向罐子中充入0.1MPa、0.3MPa、0.6MPa、0.8MPa、1.0MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，使得氢化物中H 2/CO 2的摩尔比值为12:1、4:1、2:1、1.5:1、1.2:1，使用行星式球磨机(QM-3SP4)在500转/分钟的转速下球磨反应30h，制得甲烷与氢气的混合气体。
气体的检测方法同实施例1，在质谱和气相色谱中未测得除甲烷与H 2以外的气体产物(例如CO等)。
图3是实施例3所得LaNi 5H 6分别与不同压强的CO 2混合气体球磨(500转/分钟)反应30h后，气相CO 2转化率及甲烷产率随压强的变化图。从图中可以看出，不同的H 2:CO 2摩尔比值对反应速率有影响，随着CO 2压强增大，CH 4产率降低，在0.1MPa(H 2:CO 2＝12:1)时CH 4的产率高达90％，在0.3MPa(H 2:CO 2＝4:1)时CH 4的产率为83.2％，在1.0MPa(H 2:CO 2＝1.2:1)时CH 4的产率低至47.7％。即，当H 2不足量时，反应速率慢、甲烷产率低，当H 2过量时，反应速率大大提高，但在转化率上的提高并不显著。
实施例4
(1)在0.1MPa氩气气氛的手套箱中，取2.5g经过电弧熔炼并充分破碎，过200目标准检验筛筛选的ZrNi 5粉末装入容积为25mL高温高压反应釜(NS-25-316L)中，充入4MPa的氢气，置于150℃下反应10h，使之充分活化，冷却至室温得到ZrNi 5H 6；
(2)将釜内剩余气体抽出(在抽气过程中釜内气压在0.1～1MPa之间)，在氩气手套箱中，打开反应釜取出其中的氢化产物，将其置于容积为200mL的行星球磨罐中，放入100g小钢珠(其中直径为10mm的60g，直径为6mm的40g)，将其中的氩气抽出后充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，再次抽气、充气，反复3次后，反应釜内已无杂质气体残留，分别向罐子中充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，使得氢化物中H 2/CO 2的摩尔比值为4:1，使用行星式球磨机(QM-3SP4)在500转/分钟的转速下球磨反应30h，制得甲烷与氢气的混合气体。
气体的检测方法同实施例1，在质谱和气相色谱中未测得除甲烷与H 2以外的气体产物(例如CO等)。
实施例5
(1)在0.1MPa氩气气氛的手套箱中，取2.5g经过电弧熔炼并充分破碎，过200目标准检验筛筛选的NdNi 5粉末装入容积为25mL高温高压反应釜(NS-25-316L)中，充入4MPa的氢气，置于150℃下反应10h，使之充分活化，冷却至室温得到NdNi 5H 6；
(2)将釜内剩余气体抽出(在抽气过程中釜内气压在0.1～1MPa之间)，在氩气手套箱中，打开反应釜取出其中的氢化产物，将其置于容积为200mL的行星球磨罐中，放入100g小钢珠(其中直径为10mm的60g，直径为6mm的40g)，将其中的氩气抽出后充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，再次抽气、充气，反复3次后，反应釜内已无杂质气体残留，分别向罐子中充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，使得氢化物中H 2/CO 2的摩尔比值为4:1，使用行星式球磨机(QM-3SP4)在500转/分钟的转速下球磨反应30h，制得甲烷与氢气的混合气体。
气体的检测方法同实施例1，在质谱和气相色谱中未测得除甲烷与H 2以外的气体产物(例如CO等)。
实施例6
(1)在0.1MPa氩气气氛的手套箱中，取2.5g经过电弧熔炼并充分破碎， 过200目标准检验筛筛选的PrNi 5粉末装入容积为25mL高温高压反应釜(NS-25-316L)中，充入4MPa的氢气，置于150℃下反应10h，使之充分活化，冷却至室温得到PrNi 5H 6；
(2)将釜内剩余气体抽出(在抽气过程中釜内气压在0.1～1MPa之间)，在氩气手套箱中，打开反应釜取出其中的氢化产物，将其置于容积为200mL的行星球磨罐中，放入100g小钢珠(其中直径为10mm的60g，直径为6mm的40g)，将其中的氩气抽出后充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，再次抽气、充气，反复3次后，反应釜内已无杂质气体残留，分别向罐子中充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，使得氢化物中H 2/CO 2的摩尔比值为4:1，使用行星式球磨机(QM-3SP4)在500转/分钟的转速下球磨反应30h，制得甲烷与氢气的混合气体。
气体的检测方法同实施例1，在质谱和气相色谱中未测得除甲烷与H 2以外的气体产物(例如CO等)。
实施例7
(1)在0.1MPa氩气气氛的手套箱中，取2.5g经过电弧熔炼并充分破碎，分别过200目标准检验筛筛选的SmNi 5粉末装入容积为25mL高温高压反应釜(NS-25-316L)中，充入4MPa的氢气，置于150℃下反应10h，使之充分活化，冷却至室温得到SmNi 5H 6；
(2)将釜内剩余气体抽出(在抽气过程中釜内气压在0.1～1MPa之间)，在氩气手套箱中，打开反应釜取出其中的氢化产物，将其置于容积为200mL的行星球磨罐中，放入100g小钢珠(其中直径为10mm的60g，直径为6mm的40g)，将其中的氩气抽出后充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，再次抽气、充气，反复3次后，反应釜内已无杂质气体残留，分别向罐子中充入0.3MPa含二氧化碳的混合气体(V CO2:V Ar＝19:81)，使得氢化物中H 2/CO 2的摩尔比值为4:1，使用行星式球磨机(QM-3SP4)在500转/分钟的转速下球磨反应30h，制得甲烷与氢气的混合气体。
气体的检测方法同实施例1，在质谱及气相色谱中未测得除甲烷与H 2以外的气体产物(例如CO等)。
图4为实施例3～7所得氢化物LaNi 5H 6、ZrNi 5H 6、NdNi 5H 6、PrNi 5H 6、SmNi 5H 6分别与含CO 2混合气体(0.3MPa)球磨(500转/分钟)反应30h，所得气相CO 2转化率及甲烷产率随氢化物种类变化图。图中可以看出，氢化物中LaNi 5H 6与二氧化碳作用时甲烷产率最高。
综上所述，室温下通过机械球磨储氢合金氢化物与二氧化碳气固混合物的甲烷化反应中：二氧化碳转化率几乎不随转速、气压等变化而改变；甲烷产率受转速、H 2/CO 2的摩尔以及氢化物种类影响相对较大。因此，可以选取相对适宜的转速为500转/分钟；可以根据设备条件来选择适合的含CO 2混合气体压强调整H 2/CO 2的摩尔；球磨反应时间在30h时CH 4的产率达到最大值，为最优球磨反应时间；氢化物中LaNi 5H 6与二氧化碳作用时反应速率最快，甲烷产率最高，LaNi 5H 6为最优氢化物。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (8)

  1. 一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法，其特征在于，包括以下步骤：
    在保护气氛下，将储氢合金氢化物置于球磨罐中，抽出氩气，并充入含二氧化碳的气体，在室温下，采用球磨机进行球磨反应后即制得甲烷。
  2. 根据权利要求1所述的利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法，其特征在于：
    所述储氢合金氢化物为LaNi 5H 6、ZrNi 5H 6、NdNi 5H 6、PrNi 5H 6和SmNi 5H 6中的至少一种。
  3. 根据权利要求2所述的利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法，其特征在于，所述储氢合金氢化物的制备方法为：
    在保护气氛下，将储氢合金破碎后过标准筛，然后将储氢合金在氢气气氛下进行吸氢活化反应，反应完成后冷却至室温得到储氢合金氢化物。
  4. 根据权利要求3所述的利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法，其特征在于：
    所述储氢合金为LaNi 5、ZrNi 5、NdNi 5、PrNi 5和SmNi 5中的至少一种；所述标准筛的目数为200～500目；所述氢气的压强为1～4MPa；所述吸氢活化反应为在100～200℃下反应5～10h。
  5. 根据权利要求1所述的利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法，其特征在于：
    球磨反应时，所述储氢合金氢化物中H 2与球磨罐中CO 2气体的摩尔比为1～15:1。
  6. 根据权利要求1所述的利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法，其特征在于：
    所述球磨介质和储氢合金氢化物的质量比为10～40:1。
  7. 根据权利要求1所述的利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法，其特征在于：
    所述球磨机的转速为300～500转/分钟，球磨反应时间为1～60h。
  8. 根据权利要求1所述的利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法，其特征在于：
    所述含二氧化碳的气体为纯CO 2或含CO 2和保护气氛的混合气体。
PCT/CN2019/112056 2019-07-04 2019-10-18 一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法 WO2021000456A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910600006.5A CN110357759B (zh) 2019-07-04 2019-07-04 一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法
CN201910600006.5 2019-07-04

Publications (1)

Publication Number Publication Date
WO2021000456A1 true WO2021000456A1 (zh) 2021-01-07

Family

ID=68218054

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/112056 WO2021000456A1 (zh) 2019-07-04 2019-10-18 一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法

Country Status (2)

Country Link
CN (1) CN110357759B (zh)
WO (1) WO2021000456A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110452081B (zh) * 2019-08-08 2020-06-19 华南理工大学 一种利用氢化物在室温下实现碳酸盐转换生产甲烷的方法
CN114105723B (zh) * 2021-11-26 2023-01-10 西安交通大学 一种二氧化碳通过金属氢化物转化为甲烷的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104588066A (zh) * 2014-12-19 2015-05-06 北京宝塔三聚能源科技有限公司 一种甲烷化催化剂及其制备方法
CN106316732A (zh) * 2016-08-19 2017-01-11 扬州大学 一种利用碱金属氢化物在室温机械球磨条件下还原二氧化碳制备清洁燃料的方法
US20170015549A1 (en) * 2014-04-03 2017-01-19 Saudi Basic Industries Corporation Process for converting of methane steam reforming syngas with co2
CN107188118A (zh) * 2017-06-16 2017-09-22 扬州大学 一种利用碱土金属氢化物制备氢气甲烷混合燃料的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170015549A1 (en) * 2014-04-03 2017-01-19 Saudi Basic Industries Corporation Process for converting of methane steam reforming syngas with co2
CN104588066A (zh) * 2014-12-19 2015-05-06 北京宝塔三聚能源科技有限公司 一种甲烷化催化剂及其制备方法
CN106316732A (zh) * 2016-08-19 2017-01-11 扬州大学 一种利用碱金属氢化物在室温机械球磨条件下还原二氧化碳制备清洁燃料的方法
CN107188118A (zh) * 2017-06-16 2017-09-22 扬州大学 一种利用碱土金属氢化物制备氢气甲烷混合燃料的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHONG DAN ET AL.: "Metallic Ni nanocatalyst in situ formed from LaNi5H5 toward efficient CO2 methanation", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 44, no. 55,, 20 March 2019 (2019-03-20), XP085880304, ISSN: 0360-3199, DOI: 20200301152156A *

Also Published As

Publication number Publication date
CN110357759B (zh) 2021-02-12
CN110357759A (zh) 2019-10-22

Similar Documents

Publication Publication Date Title
Lin et al. Recent advances in metastable alloys for hydrogen storage: a review
CN111892017B (zh) 一种有机液体制备高纯度高压氢气的方法
Song et al. Improvement in the hydrogen storage properties of Mg by mechanical grinding with Ni, Fe and V under H2 atmosphere
CN101476070A (zh) 一种镁基储氢合金及其制备方法
WO2021000456A1 (zh) 一种利用储氢合金氢化物在室温下实现二氧化碳甲烷化的方法
Wang et al. Striking enhanced effect of PrF3 particles on Ti3C2 MXene for hydrogen storage properties of MgH2
WO2024087463A1 (zh) 绣球花型NiO@NiMoO4复合材料及其制备和应用
CN113896167A (zh) 一种复合储氢材料、其制备方法及其应用
Li et al. Hydrogen storage properties and mechanisms of a Mg (BH4) 2· 2NH3–NaAlH4 combination system
Wang et al. Synthesis of Mg-based composite material with in-situ formed LaH3 and its hydrogen storage characteristics
CN106316732A (zh) 一种利用碱金属氢化物在室温机械球磨条件下还原二氧化碳制备清洁燃料的方法
CN103101880A (zh) 一种硼氢化锂/稀土镁基合金复合储氢材料及其制备方法
Rahman et al. Hydrogen sorption properties of Ternary Mg–Nb–O phases synthesized by solid–state reaction
CN102530872B (zh) 多元金属氨硼烷化合物储氢材料及其制备和复合放氢方法
CN109768255A (zh) 一种稀土储氢合金/硼氢化物复合储氢材料及其制备方法
ZHANG et al. Catalytic effect of two-dimensional Mo2TiC2 MXene for tailoring hydrogen storage performance of MgH2
WO2021023314A1 (zh) 一种利用氢化物在室温下实现碳酸盐转换生产甲烷的方法
Hudson et al. Studies on synthesis and dehydrogenation behavior of magnesium alanate and magnesium–sodium alanate mixture
Li et al. Enhanced hydrogen storage performance of magnesium hydride catalyzed by medium-entropy alloy CrCoNi nanosheets
WO2018215202A1 (en) Catalyst for ammonia synthesis
Cheng et al. The hydrogen storage properties of MgH 2–Fe 7 S 8 composites
CN107188118A (zh) 一种利用碱土金属氢化物制备氢气甲烷混合燃料的方法
CN109261157A (zh) 一种Ni@LaCO3OH复合材料及其制备方法和应用
CN101709396A (zh) 一种镁钛基储氢合金的制备方法
POTTMAIER VICENTE et al. Materials for hydrogen storage and the Na-Mg-BH system

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19936521

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19936521

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 27/05/2022)

122 Ep: pct application non-entry in european phase

Ref document number: 19936521

Country of ref document: EP

Kind code of ref document: A1