CN105567325A - Spinel compound-carbonate mixture system for solar energy photo-thermal chemical conversion, preparation and application thereof - Google Patents
Spinel compound-carbonate mixture system for solar energy photo-thermal chemical conversion, preparation and application thereof Download PDFInfo
- Publication number
- CN105567325A CN105567325A CN201410539425.XA CN201410539425A CN105567325A CN 105567325 A CN105567325 A CN 105567325A CN 201410539425 A CN201410539425 A CN 201410539425A CN 105567325 A CN105567325 A CN 105567325A
- Authority
- CN
- China
- Prior art keywords
- reaction
- weigh
- spinel
- cycle
- spinel compound
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 59
- 229910052596 spinel Inorganic materials 0.000 title claims description 32
- 239000011029 spinel Substances 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 title claims description 14
- 239000000126 substance Substances 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000011149 active material Substances 0.000 claims abstract description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 claims description 13
- 102000002322 Egg Proteins Human genes 0.000 claims description 13
- 108010000912 Egg Proteins Proteins 0.000 claims description 13
- 235000014103 egg white Nutrition 0.000 claims description 13
- 210000000969 egg white Anatomy 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 239000010431 corundum Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000012494 Quartz wool Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000004530 micro-emulsion Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 238000003541 multi-stage reaction Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- OIGNJSKKLXVSLS-VWUMJDOOSA-N prednisolone Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OIGNJSKKLXVSLS-VWUMJDOOSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000011734 sodium Substances 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007132 Bunsen reaction Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- -1 alkaline earth metal carbonates Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
本发明涉及一种以碳酸盐和尖晶石类化合物作为循环活性材料,通过多步法热化学循环分解水或CO2生产H2和CO的方法。主要步骤如下:1)合成出活性材料,并将两种材料混合;2)将混合的材料加热到一定温度并通入H2O或CO2,产生H2和CO;3)将2)处理后的活性材料分散于去离子水中,通入CO2进行水解,分离得到水解后的活性物种;4)将3)处理后的活性材料加热到一定温度进行放氧反应。本发明首次利用水解反应来处理产H2后的活性物种,使得产氧反应更顺利地进行,提高了该循环体系的可行性。循环体系反应温度低,利用太阳能作为热源,以H2O和CO2作为原料,清洁无污染。The present invention relates to a method for producing H2 and CO2 by splitting water or CO2 through a multi-step thermochemical cycle using carbonate and spinel-like compounds as cycle active materials. The main steps are as follows: 1) Synthesize the active material and mix the two materials; 2) Heat the mixed material to a certain temperature and feed H 2 O or CO 2 to generate H 2 and CO; 3) Treat 2) The finished active material is dispersed in deionized water, passed through CO 2 for hydrolysis, and the hydrolyzed active species is separated; 4) The active material after 3) is heated to a certain temperature for oxygen evolution reaction. The invention utilizes the hydrolysis reaction for the first time to process the active species after H2 production, so that the oxygen production reaction can be carried out more smoothly, and the feasibility of the circulation system is improved. The circulation system has a low reaction temperature, uses solar energy as a heat source, and uses H 2 O and CO 2 as raw materials, which is clean and pollution-free.
Description
技术领域technical field
本发明涉及多步法热化学循环分解水和二氧化碳。具体涉及以尖晶石类化合物与碱金属或碱土金属碳酸盐组成的混合物体系作为活性材料体系,通过多步热化学循环分解水和二氧化碳,生产氢气和一氧化碳。该体系利用太阳能作为热源,在低温(500-1000℃)下将水和二氧化碳分解,在节能减排和环境保护方面有着非常广阔的应用前景。The present invention relates to a multi-step thermochemical cycle for splitting water and carbon dioxide. It specifically involves using a mixture system composed of spinel compounds and alkali metal or alkaline earth metal carbonates as an active material system to decompose water and carbon dioxide through a multi-step thermochemical cycle to produce hydrogen and carbon monoxide. The system uses solar energy as a heat source to decompose water and carbon dioxide at low temperature (500-1000° C.), and has very broad application prospects in energy saving, emission reduction and environmental protection.
背景技术Background technique
在能源危机和环境危机的背景下,化石能源的不可持续性表现的越来越明显,过度利用化石能源所产生的温室效应、环境污染等问题日益突出,使得研究和开发清洁、环境友好的可再生能源体系迫在眉睫。我国当前是CO2排放量的第二大国,CO2排放量呈较快增长的态势,受到越来越大的环境保护压力以及国际社会压力。太阳能具有清洁无污染、取之不竭、可再生等众多优点,利用太阳能将水转化成氢气和氧气从源头上避免了污染问题,另外利用太阳能将温室气体CO2转化为便于储存的化学燃料还可以减轻温室效应。近年来,此类科学技术的开发和应用受到国际社会的广泛关注。Under the background of energy crisis and environmental crisis, the unsustainability of fossil energy is becoming more and more obvious, and the greenhouse effect and environmental pollution caused by excessive use of fossil energy are becoming more and more prominent. A renewable energy system is imminent. China is currently the second largest country in terms of CO 2 emissions, and the CO 2 emissions are growing rapidly, which is under increasing pressure from environmental protection and the international community. Solar energy has many advantages such as clean, non-polluting, inexhaustible, and renewable. Using solar energy to convert water into hydrogen and oxygen avoids pollution problems from the source. In addition, using solar energy to convert greenhouse gas CO2 into chemical fuels that are easy to store Can reduce the greenhouse effect. In recent years, the development and application of this kind of science and technology has received extensive attention from the international community.
多步热化学循环分解H2O/CO2技术是一类集太阳能转化和化学燃料生产于一体的关键技术,是当前新能源开发和研究领域的热点之一。相比两步法热化学循环1000℃以上的反应温度,多步法热化学循环具有反应温度低的明显优势,即大多数多步法热化学循环可以在1000℃以下完成。一种比较常见的多步循环模式如下:The multi-step thermochemical cycle decomposition of H 2 O/CO 2 technology is a key technology integrating solar energy conversion and chemical fuel production, and is one of the hotspots in the field of new energy development and research. Compared with the reaction temperature of the two-step thermochemical cycle above 1000 °C, the multi-step thermochemical cycle has the obvious advantage of low reaction temperature, that is, most multi-step thermochemical cycles can be completed below 1000 °C. A more common multi-step loop pattern is as follows:
H2O+A→0.5H2+AOH 2 O+A→0.5H 2 +AO
AO+B→0.5O2+ABAO+B→0.5O 2 +AB
AB→A+BAB→A+B
A物质把H2O还原,产生氢气和氧化物AO;B物质把AO氧化,产生氧气和化合物AB;第三步化合物AB在一定条件下发生复分解反应,产生A和B;通过三个反应步骤完成了循环。H2O通过此循环分解为O2和H2,此循环中H2O是唯一的输入原料,而O2和H2是产出物质。尖晶石类氧化物与碳酸盐的混合体系便是基于上述设计思路设计的一种类型的多步热化学循环。但是多步循环是多种多样的,并不仅仅局限于上述的循环模型。经典的多步循环有非金属化合物循环、金属/金属氧化物与卤素或酸循环以及金属氧化物与碱性化合物循环,其中S-I循环,Fe-Cl循环,Cu-Cl循环是比较典型的多步循环。Substance A reduces H 2 O to produce hydrogen and oxide AO; substance B oxidizes AO to produce oxygen and compound AB; in the third step, compound AB undergoes metathesis reaction under certain conditions to produce A and B; through three reaction steps The cycle is complete. H 2 O is decomposed into O 2 and H 2 through this cycle, in which H 2 O is the only input material and O 2 and H 2 are output species. The mixed system of spinel oxides and carbonates is a type of multi-step thermochemical cycle designed based on the above design ideas. But multi-step cycles are diverse and not limited to the above-mentioned cycle models. Classical multi-step cycles include non-metallic compound cycle, metal/metal oxide and halogen or acid cycle, and metal oxide and basic compound cycle, among which SI cycle, Fe-Cl cycle and Cu-Cl cycle are typical multi-step cycles cycle.
Beghi,G.E.最早提出了S-I循环(Int.J.HydrogenEnergy,1986,11(12):761-771),该循环的主要反应步骤如下图所示。其反应温度明显比两步循环低,最高反应温度仅为850℃。不过酸性体系对材料的腐蚀很大,而且HI与H2SO4的分离也是很耗能的。Zhang,Y.等(Industrial&EngineeringChemistryResearch,2014,53,3021-3028)最近对S-I循环中涉及的BunsenReaction进行了深入的研究。主要研究了SO2的流速、摩尔分数;I2含量;水含量等对液液分离过程的影响,实验结果表明当SO2的摩尔分数超过0.12,I2/H2O的摩尔比超过0.284时可以得到最佳的HI与H2SO4分离效果以及最小程度的副反应。Beghi, GE first proposed the SI cycle (Int.J.HydrogenEnergy, 1986, 11(12):761-771), the main reaction steps of this cycle are shown in the figure below. The reaction temperature is significantly lower than that of the two-step cycle, and the highest reaction temperature is only 850 °C. However, the acidic system is very corrosive to the material, and the separation of HI and H 2 SO 4 is also very energy-consuming. Zhang, Y. et al. (Industrial & Engineering Chemistry Research, 2014, 53, 3021-3028) recently conducted an in-depth study on the BunsenReaction involved in the SI cycle. Mainly studied the influence of SO 2 flow rate, mole fraction; I 2 content; water content on the liquid-liquid separation process. The experimental results showed that when the mole fraction of SO 2 exceeds 0.12 and the molar ratio of I 2 /H 2 O exceeds 0.284 Can get the best HI and H 2 SO 4 separation effect and minimal side reaction.
TolgaBalta.等(Energy,2010,35,3263-3272)详细研究了不同温度等反应条件下Cu-Cl循环四个反应步骤对整个循环系统的性能影响,并计算了产能和放能效率。该循环所面临的最大问题是酸性物质对材料的腐蚀性。TolgaBalta. et al. (Energy, 2010, 35, 3263-3272) studied in detail the influence of the four reaction steps of the Cu-Cl cycle on the performance of the entire cycle system under reaction conditions such as different temperatures, and calculated the production capacity and energy release efficiency. The biggest problem faced by this cycle is the corrosiveness of the acid to the material.
Tamaura,Y.等(SolarEnergy,1999,65,55-57)最先研究了MnFe2O4与Na2CO3的多步循环,该多步循环可以通过三步完成。该体系面临的主要问题是产氧反应动力学上不利,反应速率过慢。Seralessandri,L.等(JournalofSolidStateChemistry,2008,181,1992-1997;ScriptaMaterialia,2006,55,875-877)对该循环产氧反应进行了研究,发现产氢后反应产物的晶型结构以及CO2的分压对还原反应影响特别大。我们的重复实验结果也表明产氧反应非常不利,通常条件下很难观察到O2的产生,循环模式有待改进。Varsano,F.等(SolidStateIonics,2011,187,19-26)利用XRD技术分析了反应过程生成的各物种。他们提出产氧机理分两步进行,即CO2先与钠离子结合生成Na2CO3,钠离子被部分分离出来,使得原化合物结构塌陷,进而使得产氧反应顺利进行。总之钠离子的分离与否是能否完成产氧反应的关键所在。Kaneko,H.等(JournalofPhysicsandChemistryofSolids,2001,62,1341-1347;Energy,2001,26,919-929)采用添加Fe2O3来加速钠离子的萃出。该方法明显地促进了产氧反应,但是完成循环后如何分离残留的Fe2O3又是一个问题。Tamaura, Y. et al. (SolarEnergy, 1999, 65, 55-57) first studied the multi-step cycle of MnFe 2 O 4 and Na 2 CO 3 , which can be completed in three steps. The main problem faced by this system is that the kinetics of the oxygen generation reaction is unfavorable and the reaction rate is too slow. Seralessandri, L. et al. (Journal of Solid State Chemistry, 2008, 181, 1992-1997; Scripta Materialia, 2006, 55, 875-877) studied the cyclic oxygen production reaction and found the crystal structure of the reaction product after hydrogen production and the partial pressure of CO 2 It has a particularly large impact on the reduction reaction. The results of our repeated experiments also show that the oxygen generation reaction is very unfavorable, it is difficult to observe the generation of O2 under normal conditions, and the cycle mode needs to be improved. Varsano, F. et al. (SolidStateIonics, 2011, 187, 19-26) used XRD technology to analyze the various species generated during the reaction process. They proposed that the mechanism of oxygen generation proceeds in two steps, that is, CO 2 first combines with sodium ions to form Na 2 CO 3 , and the sodium ions are partially separated, causing the structure of the original compound to collapse, thereby enabling the oxygen generation reaction to proceed smoothly. In short, the separation of sodium ions is the key to complete the oxygen production reaction. Kaneko, H. et al. (Journal of Physics and Chemistry of Solids, 2001, 62, 1341-1347; Energy, 2001, 26, 919-929) accelerated the extraction of sodium ions by adding Fe 2 O 3 . This method obviously promotes the oxygen production reaction, but how to separate the residual Fe2O3 after the cycle is completed is another problem.
近年来,Xu,B.等(ProcNatlAcadSci,2012,109(24):9260-9264)报道了Mn3O4-Na2CO3多步循环体系。与之前相似的循环相比用Na2CO3替代NaOH减轻了体系的腐蚀强度,降低了对材料的要求。综上可知金属氧化物与碱性化合物的循环是一类有着广泛应用潜力的低温多步循环。In recent years, Xu, B. et al. (ProcNatlAcadSci, 2012, 109(24):9260-9264) reported the Mn 3 O 4 -Na 2 CO 3 multi-step cycle system. Compared with the previous similar cycle, replacing NaOH with Na 2 CO 3 reduces the corrosion strength of the system and reduces the requirements for materials. In summary, the cycle of metal oxides and basic compounds is a kind of low-temperature multi-step cycle with wide application potential.
发明内容Contents of the invention
本发明旨在提供碳酸盐(AxCO3)和尖晶石类化合物(MN2O4)混合活性材料在多步法热化学循环分解H2O或者CO2中的应用。不同碳酸盐和不同尖晶石化合物组成的混合材料可以选择性地分解H2O或者CO2中的一种或两种,同时生产H2和CO。The present invention aims to provide the application of the mixed active material of carbonate (A x CO 3 ) and spinel compound (MN 2 O 4 ) in the multi-step thermochemical cycle decomposition of H 2 O or CO 2 . The hybrid materials composed of different carbonates and different spinel compounds can selectively decompose one or both of H2O or CO2 , and simultaneously produce H2 and CO.
本发明的目的还立足于改善和优化该体系循环方式,从而提高此类循环反应体系的可行性。本发明的另一目的在于对碳酸盐和尖晶石类化合物混合材料分解水或CO2的反应参数进行优化,提供最优的反应条件。The object of the present invention is also based on improving and optimizing the circulation mode of the system, thereby improving the feasibility of this type of circulation reaction system. Another object of the present invention is to optimize the reaction parameters of the mixed material of carbonate and spinel compound to decompose water or CO 2 and provide optimal reaction conditions.
为实现上述目的,本发明提供以下方面:To achieve the above object, the present invention provides the following aspects:
本发明的碳酸盐(AxCO3)和尖晶石类化合物MN2O4混合体系,其特征在于所述的碳酸盐AxCO3中A为Li、Na、K、Be、Mg、Ca、Sr、Ba中的一种或二种以上,MN2O4中M、N为Mn、Fe、Co中的一种或者二种以上。按照3:2的摩尔比取碳酸盐与尖晶石化合物,采用直接机械研磨的混合方法进行混合,直至充分混合均匀。The mixed system of carbonate (A x CO 3 ) and spinel compound MN 2 O 4 of the present invention is characterized in that A in the carbonate A x CO 3 is Li, Na, K, Be, Mg , Ca, Sr, Ba, or one or two or more of them, M and N in MN 2 O 4 are one or two or more of Mn, Fe, and Co. Take carbonate and spinel compound according to the molar ratio of 3:2, and mix them by direct mechanical grinding until they are fully mixed.
所述尖晶石类化合物的制备方法为共沉淀水热法,高温固体反应,微乳反应,蛋清溶胶凝胶法中的一种。The preparation method of the spinel compound is one of co-precipitation hydrothermal method, high-temperature solid reaction, microemulsion reaction and egg white sol-gel method.
所述的共沉淀水热法具体步骤如下:称取M的盐MClx或者M(NO3)x0.01-50mmol,按照摩尔比N:M=2:1称取N的盐NCly或者N(NO3)y,溶解于50-300mL去离子水中,加入30mL浓度为0.1-10mol/L的NaOH溶液,搅拌均匀;转移至300mL水热釜中,反应温度范围为80℃-200℃,反应时间为3-28h;水热反应完成后冷却至室温,过滤洗涤后真空干燥6-12h,真空干燥的温度为50-80℃;The specific steps of the co-precipitation hydrothermal method are as follows: Weigh the salt of M MCl x or M(NO 3 ) x 0.01-50 mmol, and weigh the salt of N NCl y or N( NO 3 ) y , dissolved in 50-300mL deionized water, added 30mL NaOH solution with a concentration of 0.1-10mol/L, stirred evenly; 3-28h; after the completion of the hydrothermal reaction, cool to room temperature, filter and wash, then vacuum dry for 6-12h, the temperature of vacuum drying is 50-80°C;
所述的高温固体反应具体步骤如下:称取M的碳酸盐M(CO3)x0.01-50mmol,按照摩尔比N:M=2:1称取N的氧化物NyOz,在总流量为200mL/min,气体体积比为:空气(0-100%)和CO2(100-0%)的混合气氛下加热至1100℃,保持7h,原气氛保护下降温至室温;The specific steps of the high-temperature solid reaction are as follows: Weigh the M carbonate M(CO 3 ) x 0.01-50mmol, weigh the N oxide N y O z according to the molar ratio N:M=2:1, in the total The flow rate is 200mL/min, and the gas volume ratio is: heated to 1100°C in a mixed atmosphere of air (0-100%) and CO 2 (100-0%), kept for 7 hours, and cooled down to room temperature under the protection of the original atmosphere;
所述的微乳反应具体步骤如下:称取M的盐MClx或者M(NO3)x0.01-50mmol,按照摩尔比N:M=2:1称取N的盐NCly或者N(NO3)y,溶解于50-300mL去离子水中,搅拌均匀;随后加入60mL0.4M的NaDBS溶液;加入300-500mL甲苯溶液,连续搅拌12-24h,形成均匀的微乳体系;加入80mL浓度为0.1-2mol/L的NaOH溶液,继续搅拌2h;Ar保护下60-100℃老化1.5h;过滤洗涤,50-80℃干燥6-12h;320-600℃焙烧1-2h,得氧化状态尖晶石化合物。The specific steps of the microemulsion reaction are as follows: Weigh the salt of M MCl x or M(NO 3 ) x 0.01-50 mmol, and weigh the salt of N NCl y or N(NO 3 ) according to the molar ratio N:M=2:1 ) y , dissolved in 50-300mL deionized water, stirred evenly; then added 60mL 0.4M NaDBS solution; 2mol/L NaOH solution, continue stirring for 2h; aging at 60-100°C for 1.5h under Ar protection; filtering and washing, drying at 50-80°C for 6-12h; roasting at 320-600°C for 1-2h to obtain spinel compound in oxidized state .
所述的蛋清溶胶-凝胶法具体步骤如下:取30-120mL搅拌均匀的蛋清液,并加入50-200mL去离子水稀释蛋清液,称取M的盐MClx或者M(NO3)x0.01-50mmol,按照摩尔比N:M=2:1称取N的盐NCly或者N(NO3)y,将金属盐加到稀释后的蛋清液中,搅拌蒸发至胶状,转移至马弗炉中500℃条件下焙烧5h,得氧化状态的尖晶石化合物。The specific steps of the egg white sol-gel method are as follows: Take 30-120mL of egg white liquid that has been stirred evenly, and add 50-200mL of deionized water to dilute the egg white liquid, weigh the salt of M MCl x or M(NO 3 ) x 0.01 -50mmol, weigh N salt NCl y or N(NO 3 ) y according to the molar ratio N:M=2:1, add the metal salt to the diluted egg white, stir and evaporate until gelatinous, transfer to muffle Calcined in a furnace at 500°C for 5 hours to obtain the spinel compound in the oxidized state.
所述的碳酸盐和尖晶石类化合物混合体系可应用于H2O和CO2的多步分解,该过程由以下多个反应步骤组成:The described mixed system of carbonate and spinel compounds can be applied to the multi-step decomposition of H2O and CO2 , which consists of the following multiple reaction steps:
a.合成出尖晶石化合物MN2O4,利用研磨等方法使碳酸盐与尖晶石类化合物两种材料混合在一起;a. Synthesize the spinel compound MN 2 O 4 , and use grinding and other methods to mix the two materials of carbonate and spinel compound together;
b.将混合的活性材料体系在Ar气氛下加热到500~1000℃,恒温处理2-3h后,由Ar带入H2O或CO2中的一种或两种;或由CO2带入H2O;或单独通入CO2;产生H2和CO;b. Heating the mixed active material system to 500-1000°C under an Ar atmosphere, and after constant temperature treatment for 2-3 hours, one or both of H 2 O or CO 2 is brought into by Ar; or brought into by CO 2 H 2 O; or feed CO 2 alone; generate H 2 and CO;
c.将b处理后的活性材料分散在水中,得到活性材料的含量为1-10wt%的混合液,连续搅拌并通入CO2进行水解反应,分离干燥得到水解后的活性物种;c. Dispersing the active material treated in b in water to obtain a mixed solution with an active material content of 1-10 wt%, stirring continuously and introducing CO2 for hydrolysis reaction, separating and drying to obtain the hydrolyzed active species;
d.将c处理后的活性物种在Ar气氛下加热到500~1000℃,进行放氧反应,完成产氧产氢循环。d. Heating the active species treated in c to 500-1000° C. under an Ar atmosphere to perform an oxygen evolution reaction and complete the cycle of oxygen and hydrogen production.
该循环反应的产氢产氧反应是在固定床反应器内进行的。The hydrogen production and oxygen production reaction of the cycle reaction is carried out in a fixed bed reactor.
所述固定床反应器的组成结构为:包括一石英管,石英管内设有上端开口、底部带孔的刚玉坩埚,刚玉坩埚下方设有一支撑石英管,刚玉坩埚通过其下方的支撑石英管定位于外石英管内的特位置,刚玉坩埚的内部底端孔的上方设有石英棉,石英棉上铺设Al2O3填料,Al2O3填料上装填有活性材料,依次再用Al2O3填料、石英棉封存。The composition and structure of the fixed bed reactor is as follows: comprising a quartz tube, a corundum crucible with an upper end opening and a hole in the bottom is provided in the quartz tube, a supporting quartz tube is arranged below the corundum crucible, and the corundum crucible is positioned on the At a special position inside the outer quartz tube, quartz wool is placed above the inner bottom hole of the corundum crucible, and Al 2 O 3 fillers are laid on the quartz wool, and active materials are filled on the Al 2 O 3 fillers, followed by Al 2 O 3 fillers. , Quartz wool storage.
本发明具有以下优点:The present invention has the following advantages:
1.本发明首次利用水解反应处理产H2后的活性物种,改善了产氧反应的动力学性质,大大提高了产氧反应速率,使得产氧反应可以更顺利地进行,提高了该循环体系的可行性。1. For the first time, the present invention utilizes hydrolysis reaction to treat active species after producing H 2 , which improves the kinetic properties of oxygen production reaction, greatly increases the rate of oxygen production reaction, makes oxygen production reaction proceed more smoothly, and improves the circulation system feasibility.
2.本发明的活性材料体系可以在较低的还原温度下(500-1000℃)完成产氧反应。2. The active material system of the present invention can complete the oxygen generation reaction at a relatively low reduction temperature (500-1000° C.).
3.本发明提供的活性材料体系,可以利用聚焦太阳能产生的高温热量作为能量来源,以H2O或者CO2作为反应原料,产生H2和CO,无其他任何副产物,是可持续和清洁无污染的能量转化体系。3. The active material system provided by the present invention can use high-temperature heat generated by concentrated solar energy as an energy source, and use H 2 O or CO 2 as a reaction raw material to generate H 2 and CO without any other by-products, which is sustainable and clean Pollution-free energy conversion system.
附图说明Description of drawings
图1所示是固定床反应器的结构简图,其中1:石英管;2:支撑石英管;3:密封接头;4:刚玉坩埚;5:活性材料。Figure 1 is a schematic diagram of the structure of a fixed-bed reactor, where 1: quartz tube; 2: supporting quartz tube; 3: sealing joint; 4: corundum crucible; 5: active material.
图2为不同水热时间合成的MnFe2O4XRD图,XRD衍射峰表明合成的MnFe2O4具有典型的尖晶石结构。Figure 2 is the XRD pattern of MnFe 2 O 4 synthesized at different hydrothermal times, and the XRD diffraction peaks show that the synthesized MnFe 2 O 4 has a typical spinel structure.
图3为MnFe2O4&Na2CO3产氢速率-时间变化曲线,积分得氢气产量34.9mlH2/gMnFe2O4。Figure 3 is the hydrogen production rate-time curve of MnFe 2 O 4 &Na 2 CO 3 , and the hydrogen production is 34.9mlH 2 /gMnFe 2 O 4 by integration.
图4为水解产物产氧速率-时间变化曲线,积分得氧气产量16.2mlO2/g水解产物。Fig. 4 is the oxygen production rate-time curve of the hydrolyzate, and the oxygen production is 16.2mlO 2 /g hydrolyzate by integration.
图5为循环产物XRD图,XRD衍射峰证实产氢、产氧循环反应后MnFe2O4得以再生。Figure 5 is the XRD pattern of the cycle product, and the XRD diffraction peaks confirm that MnFe 2 O 4 is regenerated after the cycle reaction of hydrogen production and oxygen production.
图6为活性材料MnFe2O4&Na2CO3水解产物产氧曲线,积分后得氧气产量17.1mlO2/g水解产物。Figure 6 is the oxygen production curve of the active material MnFe 2 O 4 &Na 2 CO 3 hydrolyzate. After integration, the oxygen production is 17.1mlO 2 /g hydrolyzate.
具体实施方式detailed description
固定床反应器结构简图见附图1。应用时,取大约0.2g混合活性材料置于刚玉坩埚内,样品装填方式如上所述,反应器材质为石英管,反应管(石英管)内径为17mm,反应产物用气相色谱进行在线分析。实施例1A schematic diagram of the structure of the fixed-bed reactor is shown in Figure 1. During application, about 0.2g of the mixed active material is placed in a corundum crucible, the sample filling method is as described above, the material of the reactor is a quartz tube, and the inner diameter of the reaction tube (quartz tube) is 17mm, and the reaction product is analyzed online by gas chromatography. Example 1
称取1.9791g氯化锰(10mmol)、5.4058g氯化铁(20mmol)溶解于200ml去离子水中,室温下搅拌30min;称取4.8gNaOH溶解于30ml去离子水中;持续搅拌下将NaOH溶液滴加到金属盐溶液中,继续搅拌30min至均匀;转移至300ml水热釜中180℃水热反应3h;过滤洗涤,60℃真空干燥6h,得尖晶石化合物MnFe2O4。将水热处理时间分别设为5h、6h、8h、12h、14h、18h、24h、28h得不同时间水热合成的MnFe2O4材料,XRD图显示该系列MnFe2O4材料具有典型的尖晶石结构(附图2)。按照3:2的摩尔比称取Na2CO3和6h水热合成的MnFe2O4材料,采用直接机械研磨的混合方法进行混合,多次研磨,直至充分混合均匀。Weigh 1.9791g manganese chloride (10mmol), 5.4058g ferric chloride (20mmol) and dissolve in 200ml deionized water, stir at room temperature for 30min; weigh 4.8gNaOH and dissolve in 30ml deionized water; add NaOH solution dropwise under continuous stirring Add to the metal salt solution, continue to stir for 30 minutes until uniform; transfer to a 300ml hydrothermal kettle for hydrothermal reaction at 180°C for 3h; filter and wash, and vacuum dry at 60°C for 6h to obtain the spinel compound MnFe 2 O 4 . The hydrothermal treatment time was set to 5h, 6h, 8h, 12h, 14h, 18h, 24h, 28h to obtain the MnFe 2 O 4 materials hydrothermally synthesized at different times. The XRD pattern shows that this series of MnFe 2 O 4 materials have typical spinel Stone structure (figure 2). According to the molar ratio of 3:2, Na 2 CO 3 and 6h hydrothermally synthesized MnFe 2 O 4 materials were weighed, mixed by direct mechanical grinding mixing method, and ground several times until fully mixed and uniform.
实施例2Example 2
称取1.9791g氯化锰(10mmol)、5.4058g氯化铁(20mmol)溶解于200ml去离子水中,室温下搅拌30min;称取3.2gNaOH,溶解于30ml去离子水中;持续搅拌下将NaOH溶液滴加到金属盐溶液中,继续搅拌30min至均匀;转移至300ml水热釜中180℃反应6h;过滤洗涤,60℃真空干燥6h,得尖晶石化合物MnFe2O4。改变NaOH的用量,分别称取4.8g、6.4g、8.0g、9.6gNaOH,按上述方法处理后得不同碱浓度水热合成的MnFe2O4材料。按照3:2的摩尔比称取Na2CO3和加入3.2gNaOH合成的MnFe2O4材料,采用直接机械研磨的混合方法进行混合,多次研磨,直至充分混合均匀。Weigh 1.9791g manganese chloride (10mmol), 5.4058g ferric chloride (20mmol) and dissolve in 200ml deionized water, stir at room temperature for 30min; weigh 3.2gNaOH, dissolve in 30ml deionized water; drop NaOH solution under continuous stirring Add it to the metal salt solution, and continue to stir for 30 minutes until uniform; transfer it to a 300ml hydrothermal kettle for 6 hours at 180°C; filter and wash, and vacuum dry at 60°C for 6 hours to obtain the spinel compound MnFe 2 O 4 . Change the amount of NaOH, weigh 4.8g, 6.4g, 8.0g, and 9.6g NaOH respectively, and treat them according to the above method to obtain MnFe 2 O 4 materials hydrothermally synthesized with different alkali concentrations. According to the molar ratio of 3:2, Na 2 CO 3 and MnFe 2 O 4 materials synthesized by adding 3.2g of NaOH were weighed, mixed by direct mechanical grinding mixing method, and ground several times until fully mixed and uniform.
实施例3Example 3
称取1.9791g氯化锰(10mmol)、5.4058g氯化铁(20mmol)溶解于200ml去离子水中,室温下搅拌30min;称取4.8gNaOH,溶解于30ml去离子水中;持续搅拌下将NaOH溶液滴加到金属盐溶液中,继续搅拌30min至均匀;转移至300ml水热釜中,160℃反应6h;过滤洗涤,60℃真空干燥6h,得尖晶石化合物MnFe2O4。改变水热处理温度,分别设为80℃、100℃、120℃、140℃、180℃、200℃,按上述方法处理后得不同温度水热合成的MnFe2O4材料。按照3:2的摩尔比称取Na2CO3和160℃水热合成的MnFe2O4材料,采用直接机械研磨的混合方法进行混合,多次研磨,直至充分混合均匀。Weigh 1.9791g manganese chloride (10mmol), 5.4058g ferric chloride (20mmol) and dissolve in 200ml deionized water, stir at room temperature for 30min; weigh 4.8gNaOH, dissolve in 30ml deionized water; drop the NaOH solution under continuous stirring Add it to the metal salt solution, and continue to stir for 30 minutes until uniform; transfer it to a 300ml hydrothermal kettle, and react at 160°C for 6h; filter and wash, and vacuum dry at 60°C for 6h to obtain the spinel compound MnFe 2 O 4 . Change the hydrothermal treatment temperature and set it to 80°C, 100°C, 120°C, 140°C, 180°C, 200°C respectively, and obtain MnFe 2 O 4 materials hydrothermally synthesized at different temperatures after treatment according to the above method. According to the molar ratio of 3:2, Na 2 CO 3 and 160°C hydrothermally synthesized MnFe 2 O 4 materials were weighed, mixed by direct mechanical grinding, and ground several times until fully mixed.
实施例4Example 4
称取1.1495gMnCO3(10mmol)和1.5969gFe2O3(10mmol),用研钵混合均匀,并充分研磨。在25%空气&75%CO2的气氛下以20℃/min的加热速率加热至1100℃,保持7小时,原气氛保护下降温至室温。所得产物研磨均匀后得MnFe2O4材料。改变空气(0-100%)与CO2(100-0%)的体积比,得一系列不同气氛下合成的MnFe2O4材料。按照3:2的摩尔比称取Na2CO3和25%空气&75%CO2的气氛下合成的MnFe2O4材料,采用直接机械研磨的混合方法进行混合,多次研磨,直至充分混合均匀。Weigh 1.1495g MnCO 3 (10mmol) and 1.5969g Fe 2 O 3 (10mmol), mix them uniformly with a mortar, and grind them thoroughly. In an atmosphere of 25% air & 75% CO 2 , it was heated to 1100°C at a heating rate of 20°C/min, kept for 7 hours, and cooled down to room temperature under the protection of the original atmosphere. The obtained product is ground uniformly to obtain MnFe 2 O 4 material. By changing the volume ratio of air (0-100%) and CO 2 (100-0%), a series of MnFe 2 O 4 materials synthesized under different atmospheres are obtained. Weigh Na 2 CO 3 and MnFe 2 O 4 materials synthesized under the atmosphere of 25% air & 75% CO 2 according to the molar ratio of 3:2, and mix them by direct mechanical grinding mixing method, and grind them several times until they are fully mixed and uniform .
实施例5Example 5
取30ml搅拌均匀的蛋清液,加入50ml去离子水稀释蛋清液,按照1:2的摩尔比例称取3.579g硝酸锰(20mmol)和16.16g硝酸铁(40mmol),搅拌下将金属盐加入稀释后的蛋清液中,搅拌均匀后蒸发至胶状,转移至马弗炉中500℃下焙烧5小时,得海绵状的尖晶石化合物MnFe2O4材料。按照3:2的摩尔比称取Na2CO3和MnFe2O4材料,采用直接机械研磨的混合方法进行混合,多次研磨,直至充分混合均匀。Take 30ml of evenly stirred egg white, add 50ml of deionized water to dilute the egg white, weigh 3.579g of manganese nitrate (20mmol) and 16.16g of ferric nitrate (40mmol) according to the molar ratio of 1:2, add the metal salt after stirring Egg white liquid, stirred evenly, evaporated to gel, transferred to a muffle furnace at 500°C and baked for 5 hours to obtain a spongy spinel compound MnFe 2 O 4 material. Weigh the Na 2 CO 3 and MnFe 2 O 4 materials according to the molar ratio of 3:2, mix them by direct mechanical grinding, and grind them several times until they are fully mixed.
实施例6Example 6
按照1:2的摩尔比例称取1.7895g硝酸锰(10mmol)和8.080g硝酸铁(20mmol),将其溶解于50ml去离子水中,搅拌均匀;随后加入60ml0.4M的NaDBS溶液;加入500ml甲苯溶液,连续搅拌24小时,形成均匀的微乳体系;加入80ml的浓度为1mol/L的NaOH溶液,继续搅拌2h;Ar保护下100℃老化1.5h;过滤洗涤干燥;500℃焙烧得氧化状态尖晶石化合物MnFe2O4材料。按照3:2的摩尔比称取Na2CO3和MnFe2O4材料,采用直接机械研磨的混合方法进行混合,多次研磨,直至充分混合均匀。Weigh 1.7895g of manganese nitrate (10mmol) and 8.080g of ferric nitrate (20mmol) according to the molar ratio of 1:2, dissolve them in 50ml of deionized water, stir well; then add 60ml of 0.4M NaDBS solution; add 500ml of toluene solution , continuously stirred for 24 hours to form a uniform microemulsion system; added 80ml of NaOH solution with a concentration of 1mol/L, and continued to stir for 2h; aged at 100°C for 1.5h under the protection of Ar; filtered, washed and dried; roasted at 500°C to obtain oxidized spinels Petroleum compound MnFe 2 O 4 material. Weigh the Na 2 CO 3 and MnFe 2 O 4 materials according to the molar ratio of 3:2, mix them by direct mechanical grinding, and grind them several times until they are fully mixed.
实施例7Example 7
称取约0.2g实施例1中6h水热合成的MnFe2O4与Na2CO3机械研磨后的混合材料,装样后置于反应管内。在Ar气氛下以20℃/min的升温速率从室温加热到800℃,恒温处理2.5h后,通入水蒸气,反应温度保持在800℃,产氢反应在3h内结束。附图3是实施例1中水热6h合成的MnFe2O4产氢反应的速率-时间变化曲线。将产氢后的反应产物取出,研磨均匀后分散于去离子水中,其中固体粉末含量为2wt%。将该混合液加热到80℃,连续搅拌并通入CO2的条件下水解反应3h,将水解所得的固体产物分离,真空干燥。称取水解所得的活性物种0.4g,装样后置于反应管内,在Ar气氛下以20℃/min的升温速率从室温加热到800℃,进行产氧反应,恒温处理30min产氧反应完成。附图4是施例1中水热6h合成的MnFe2O4产氢反应后水解产物的产氧反应速率-时间变化曲线。活性材料通过产氢、产氧循环完成再生,再生后的MnFe2O4依次再进行产氢、产氧循环反应。循环反应产物的XRD图表明循环后活性材料得以再生(附图5)。Weigh about 0.2 g of the mechanically ground mixed material of MnFe 2 O 4 and Na 2 CO 3 hydrothermally synthesized in Example 1 for 6 hours, and place the sample in the reaction tube after loading. Heated from room temperature to 800°C at a rate of 20°C/min under Ar atmosphere, and after constant temperature treatment for 2.5 hours, water vapor was introduced to keep the reaction temperature at 800°C, and the hydrogen production reaction ended within 3 hours. Accompanying drawing 3 is the rate-time variation curve of the hydrogen production reaction of MnFe 2 O 4 synthesized by hydrothermal 6h in Example 1. The reaction product after hydrogen production was taken out, ground uniformly, and then dispersed in deionized water, wherein the solid powder content was 2 wt%. The mixture was heated to 80° C., continuously stirred and hydrolyzed for 3 h under the condition of introducing CO 2 , and the solid product obtained by hydrolysis was separated and dried in vacuo. Weigh 0.4 g of the active species obtained by hydrolysis, put the sample into the reaction tube, and heat it from room temperature to 800 °C at a rate of 20 °C/min under Ar atmosphere to carry out the oxygen generation reaction. The oxygen generation reaction is completed after constant temperature treatment for 30 minutes. Accompanying drawing 4 is the oxygen production reaction rate-time variation curve of the hydrolyzed product after hydrothermal synthesis of MnFe 2 O 4 hydrogen production reaction in Example 1 for 6 hours. The active material is regenerated through hydrogen production and oxygen production cycles, and the regenerated MnFe 2 O 4 undergoes hydrogen production and oxygen production cycle reactions in turn. The XRD pattern of the cycled reaction product indicated that the active material was regenerated after the cycle (Fig. 5).
实施例8Example 8
称取约0.2g实施例5所得的混合材料,装样后置于反应管内。在Ar气氛下以20℃/min的升温速率加热到800℃,恒温处理2.5h后,降温至室温。将反应产物取出研磨后分散于50ml去离子水中,通入CO2,80℃温度下水解反应3h,分离干燥得水解产物。将水解产物装回原反应管,在Ar气氛下以20℃/min的升温速率加热到800℃,进行产氧反应,恒温处理30min产氧反应结束(附图6)。产氧后产物同实施例7处理,进行产氢产氧循环反应。Weigh about 0.2 g of the mixed material obtained in Example 5, and place it in the reaction tube after loading the sample. Heated to 800°C at a heating rate of 20°C/min under Ar atmosphere, and cooled to room temperature after constant temperature treatment for 2.5h. The reaction product was taken out and ground, dispersed in 50 ml of deionized water, introduced with CO 2 , hydrolyzed at 80° C. for 3 h, separated and dried to obtain the hydrolyzed product. The hydrolyzate was put back into the original reaction tube, and heated to 800° C. under an Ar atmosphere at a heating rate of 20° C./min to carry out an oxygen generation reaction, and the oxygen generation reaction was completed after 30 minutes of constant temperature treatment (Fig. 6). The product after oxygen generation was treated in the same way as in Example 7, and the cycle reaction of hydrogen and oxygen generation was carried out.
综上所述,本发明合成了一系列尖晶石类型(MN2O4)化合物,这类材料与碳酸盐(AxCO3)混合后可以通过多步法反应将H2O或者CO2分解为H2和CO。本发明专利进一步改进和发展了碳酸盐(AxCO3)和尖晶石类化合物(MN2O4)体系多步热化学循环方式,首次利用水解反应来处理产H2后的活性物种,使得产氧反应更顺利地进行,提高了该循环体系的可行性。本发明的多步法热化学循环体系,反应温度低(500-1000℃),可以利用聚焦太阳能产生的高温热量作为能量来源,以H2O和CO2作为输入原料,产出H2和CO,清洁无污染,有望成为通过太阳能还原H2O和CO2,制备化学燃料(合成气)的有效技术。In summary, the present invention synthesized a series of spinel-type (MN 2 O 4 ) compounds, which can be mixed with carbonate (A x CO 3 ) to convert H 2 O or CO into 2 decomposes into H2 and CO. The patent of the present invention further improves and develops the multi-step thermochemical cycle mode of the carbonate (A x CO 3 ) and spinel compound (MN 2 O 4 ) system, and uses hydrolysis reaction for the first time to treat the active species after H 2 production , making the oxygen production reaction proceed more smoothly and improving the feasibility of the cycle system. The multi-step thermochemical cycle system of the present invention has a low reaction temperature (500-1000°C), can use high-temperature heat generated by focused solar energy as an energy source, and use H2O and CO2 as input materials to produce H2 and CO , clean and pollution-free, it is expected to become an effective technology for the reduction of H 2 O and CO 2 by solar energy to prepare chemical fuel (synthesis gas).
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410539425.XA CN105567325B (en) | 2014-10-11 | 2014-10-11 | It is a kind of for the catalytic removal of nox of solar energy thermochemical study and the mixture system of carbonate and its preparation and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410539425.XA CN105567325B (en) | 2014-10-11 | 2014-10-11 | It is a kind of for the catalytic removal of nox of solar energy thermochemical study and the mixture system of carbonate and its preparation and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105567325A true CN105567325A (en) | 2016-05-11 |
CN105567325B CN105567325B (en) | 2018-09-21 |
Family
ID=55877967
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410539425.XA Active CN105567325B (en) | 2014-10-11 | 2014-10-11 | It is a kind of for the catalytic removal of nox of solar energy thermochemical study and the mixture system of carbonate and its preparation and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105567325B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110155941A (en) * | 2019-05-24 | 2019-08-23 | 山东大学 | A thermochemical cycle-based microwave heating hydrogen production device, hydrogen production method and application |
CN115504811A (en) * | 2022-09-09 | 2022-12-23 | 昆明理工大学 | A Method for Permanently Sequestering CO2 Using Solar Photothermal Catalytic Minerals |
CN115990500A (en) * | 2022-12-29 | 2023-04-21 | 中国民航大学 | Method for synthesizing pentafluoroidine through co-conversion of iodine |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1121101A (en) * | 1997-06-30 | 1999-01-26 | Yutaka Tamaura | Production of hydrogen and hydrogen-generating reaction agent |
CN1333179A (en) * | 2000-07-11 | 2002-01-30 | 中南大学 | Wet chemical synthesizing method for lithium-manganese oxide |
CN1554569A (en) * | 2003-12-25 | 2004-12-15 | 吴佶伟 | System and its device for producing hydrogen and oxygen using solar energy |
CN101100372A (en) * | 2007-07-03 | 2008-01-09 | 哈尔滨工程大学 | Preparation method of spinel ferrite powder |
WO2013151973A1 (en) * | 2012-04-06 | 2013-10-10 | California Institute Of Technology | New methods and materials for the thermochemical production of hydrogen from water |
-
2014
- 2014-10-11 CN CN201410539425.XA patent/CN105567325B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1121101A (en) * | 1997-06-30 | 1999-01-26 | Yutaka Tamaura | Production of hydrogen and hydrogen-generating reaction agent |
CN1333179A (en) * | 2000-07-11 | 2002-01-30 | 中南大学 | Wet chemical synthesizing method for lithium-manganese oxide |
CN1554569A (en) * | 2003-12-25 | 2004-12-15 | 吴佶伟 | System and its device for producing hydrogen and oxygen using solar energy |
CN101100372A (en) * | 2007-07-03 | 2008-01-09 | 哈尔滨工程大学 | Preparation method of spinel ferrite powder |
WO2013151973A1 (en) * | 2012-04-06 | 2013-10-10 | California Institute Of Technology | New methods and materials for the thermochemical production of hydrogen from water |
Non-Patent Citations (2)
Title |
---|
Y. TAMAURA等: "Solar Hydrogen Production By Using Ferrites", 《SOLAR ENERGY》 * |
张雄: "《建筑功能外加剂》", 31 January 2004, 化学工业出版社 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110155941A (en) * | 2019-05-24 | 2019-08-23 | 山东大学 | A thermochemical cycle-based microwave heating hydrogen production device, hydrogen production method and application |
CN115504811A (en) * | 2022-09-09 | 2022-12-23 | 昆明理工大学 | A Method for Permanently Sequestering CO2 Using Solar Photothermal Catalytic Minerals |
CN115504811B (en) * | 2022-09-09 | 2023-09-22 | 昆明理工大学 | Solar photo-thermal catalytic mineral permanent CO sealing 2 Is a method of (2) |
CN115990500A (en) * | 2022-12-29 | 2023-04-21 | 中国民航大学 | Method for synthesizing pentafluoroidine through co-conversion of iodine |
Also Published As
Publication number | Publication date |
---|---|
CN105567325B (en) | 2018-09-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109806902B (en) | A kind of preparation method of W18O49/NiWO4/NF self-supporting electrocatalytic material | |
CN112495401B (en) | A Mo-doped MoO3@ZnIn2S4 Z system photocatalyst and its preparation method and application | |
CN101219783B (en) | Method for producing electrode material with ferrophosphorus | |
CN103111302A (en) | Preparation and application of shell-core-type perovskite-wrapping hydrotalcite-like-based oxide reforming hydrogen production catalyst | |
CN111790412B (en) | Method for producing carbon compound by reducing carbon dioxide | |
CN108609643B (en) | Perovskite oxides and their preparation and application in solar photothermochemical conversion | |
CN106012018A (en) | Preparation method for bismuth vanadate mesoporous single crystal | |
CN105567325B (en) | It is a kind of for the catalytic removal of nox of solar energy thermochemical study and the mixture system of carbonate and its preparation and application | |
CN105070902A (en) | Mixed transition metal based preparation method for cathode material of sodium secondary battery | |
CN103464134B (en) | Carbon dioxide decomposition prepares the catalyst of carbon monoxide and method for making and application | |
CN103172021A (en) | Application of CeO2-based active materials in the decomposition of H2O and/or CO2 in a two-step thermochemical cycle | |
CN116713009A (en) | Preparation method and application of ZnCdS/NiO composite photocatalyst | |
CN107774269A (en) | Co deposited synthesis copper ceria catalyst, preparation method and application | |
CN111215085B (en) | Two-step solar thermochemical energy storage non-noble metal catalyst and its preparation and application | |
CN111204812A (en) | Preparation method of metal cation-doped modified lithium ion sieve | |
CN116351438B (en) | Cerium oxide indium sulfide photocatalytic material and preparation method and application thereof | |
CN117482965A (en) | Photocatalytic reduction of CO 2 Catalyst for preparing methane and preparation method thereof | |
CN106006747A (en) | A kind of method and product thereof for easily preparing Mn3O4 nanopowder | |
CN117427644A (en) | Co for low-temperature CO catalytic oxidation 3 O 4 -CeO 2 Catalyst and preparation method thereof | |
CN114904511A (en) | Based on SmMnO 3 CO of perovskite 2 Method for producing thermochemically transformed materials and use thereof | |
CN111468133B (en) | Preparation method of potassium niobate/alpha-ferric oxide heterogeneous photocatalyst | |
CN103145190A (en) | A kind of method for preparing Ca2Fe2O5 nanopowder | |
CN102730760A (en) | Preparation method of 1*1-type manganese oxide octahedral molecular sieves | |
CN114762829A (en) | Simple preparation method of Z-type heterojunction photocatalytic material | |
CN112516990A (en) | Synthetic method and application of layered perovskite type photocatalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |