CN103789061A - Cobalt-based composite oxygen carrier and preparation method thereof - Google Patents
Cobalt-based composite oxygen carrier and preparation method thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000001301 oxygen Substances 0.000 title claims abstract description 60
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 60
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 20
- 239000010941 cobalt Substances 0.000 title claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 title abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000011240 wet gel Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 7
- 239000000203 mixture Substances 0.000 claims 3
- 230000004913 activation Effects 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000012216 screening Methods 0.000 claims 2
- 238000010792 warming Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229910020599 Co 3 O 4 Inorganic materials 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Gas Separation By Absorption (AREA)
Abstract
本发明公开了一种钴基复合载氧体及其制备方法。所述载氧体由Co3O4和CuO组成，其中Co3O4的质量百分数为95%，CuO的质量百分数为5%。本发明采用溶胶凝胶法，控制适宜的反应条件，制备出粒径均匀，分散度好的钴基复合载氧体；本发明钴基复合载氧体的制备方法简单，制备出的复合载氧体具有较快的反应速率，释氧速率得到明显提升。
The invention discloses a cobalt-based composite oxygen carrier and a preparation method thereof. The oxygen carrier is composed of Co 3 O 4 and CuO, wherein the mass percentage of Co 3 O 4 is 95%, and the mass percentage of CuO is 5%. The present invention adopts the sol-gel method, controls suitable reaction conditions, and prepares the cobalt-based composite oxygen carrier with uniform particle size and good dispersion; the preparation method of the cobalt-based composite oxygen carrier of the present invention is simple, and the prepared composite oxygen carrier The body has a faster reaction rate, and the oxygen release rate is significantly improved.
Description
技术领域technical field
本发明属于化学链氧解耦系统中载氧体颗粒的制备技术领域。具体涉及一种复合氧化物载氧体及其制备方法。The invention belongs to the technical field of preparation of oxygen carrier particles in a chemical chain oxygen decoupling system. It specifically relates to a composite oxide oxygen carrier and a preparation method thereof.
背景技术Background technique
能源有效利用与环境相容协调发展是21世纪全世界都极为关注的热点和难点，减排CO2的努力已经成为各国能源决策的一个关键因素，迄今为止，当前能源动力系统回收CO2的难题主要表现在：化石燃料排放的CO2数量巨大，而且直接燃烧的产物中CO2常常被氮气稀释，分离与捕集成本较高，系统能效显著降低，同时也会产生NOx、SO2等其他污染物。用传统分离过程回收需要消耗大量的能源，导致动力系统效率大幅度降低（减小5%～15%）。化学链燃烧技术作为新一代洁净、高效燃烧技术，可以实现CO2内分离和避免NOx污染物产生，且可实现化学能的梯级利用，已成为世界能源、环境问题研究的重要方向。The efficient utilization of energy and the compatible and coordinated development of the environment are the hotspots and difficulties that the whole world pays close attention to in the 21st century. Efforts to reduce CO2 emissions have become a key factor in energy decision-making in various countries. The main manifestations are: the amount of CO 2 emitted by fossil fuels is huge, and the CO 2 in the direct combustion product is often diluted by nitrogen, the cost of separation and capture is high, the energy efficiency of the system is significantly reduced, and other pollutants such as NO x and SO 2 are also produced pollutants. Recycling with the traditional separation process consumes a lot of energy, resulting in a significant reduction in the efficiency of the power system (reduction of 5% to 15%). As a new generation of clean and efficient combustion technology, chemical looping combustion technology can realize the separation of CO 2 and avoid the generation of NO x pollutants, and can realize the cascade utilization of chemical energy. It has become an important direction of research on energy and environmental issues in the world.
化学链燃烧的基本原理是将传统的燃料与空气直接接触反应的燃烧借助于载氧体的作用分解为两个气固反应，燃料与空气无需接触，由载氧体将空气中的氧传递到燃料中。化学链燃烧系统由氧化反应器、还原反应器和载氧体组成。固体载氧体在2个反应器之间循环，实现氧的转移。载氧体在两个反应器之间循环使用，一方面通过在氧化反应器的氧化反应为还原反应器的还原反应提供氧，另一方面将氧化反应器的氧化反应中产生的热量传递给还原反应器。化学链循环过程，伴随的就是载氧体的氧化和还原。因此，载氧体的物理和化学性质是实现不同燃料化学链燃烧的关键所在。The basic principle of chemical looping combustion is to decompose the traditional combustion of direct contact reaction between fuel and air into two gas-solid reactions with the help of oxygen carrier. There is no need for contact between fuel and air, and the oxygen carrier transfers the oxygen in the air to in fuel. The chemical looping combustion system is composed of oxidation reactor, reduction reactor and oxygen carrier. The solid oxygen carrier circulates between the two reactors to realize the transfer of oxygen. The oxygen carrier is recycled between the two reactors. On the one hand, it provides oxygen for the reduction reaction of the reduction reactor through the oxidation reaction in the oxidation reactor, and on the other hand, it transfers the heat generated in the oxidation reaction of the oxidation reactor to the reduction reaction. reactor. The chemical chain cycle process is accompanied by the oxidation and reduction of the oxygen carrier. Therefore, the physical and chemical properties of oxygen carriers are the key to realize chemical looping combustion of different fuels.
目前，载氧体的主要研究集中在Ni、Fe、Cu、Co、Mn等过渡金属的氧化物，以及硫酸盐载氧体和钙钛矿型载氧体等。金属氧化物载氧体由于具有较高的反应性和耐高温的优点而受到了广泛的关注，但还存在着释氧速率不够快等缺点。At present, the main research on oxygen carriers focuses on the oxides of transition metals such as Ni, Fe, Cu, Co, Mn, etc., as well as sulfate oxygen carriers and perovskite oxygen carriers. Metal oxide oxygen carriers have attracted extensive attention due to their high reactivity and high temperature resistance, but there are also disadvantages such as insufficient oxygen release rate.
发明内容Contents of the invention
本发明的目的在于克服现有技术存在的缺点，提供一种钴基复合载氧体颗粒及其制备方法。钴基载氧体经连续释氧吸氧后仍能保持较好的活性，和铁基载氧体相比具有较好的反应性，但钴基载氧体解耦氧时吸热量大，很难应用于氧解耦化学链燃烧技术。在钴基载氧体颗粒中添加CuO，通过溶胶凝胶法得到粒径均匀，反应速率较快的钴基复合载氧体。The purpose of the present invention is to overcome the shortcomings of the prior art, and provide a cobalt-based composite oxygen carrier particle and a preparation method thereof. The cobalt-based oxygen carrier can still maintain good activity after continuous oxygen release and oxygen absorption. Compared with the iron-based oxygen carrier, it has better reactivity. It is difficult to apply to oxygen decoupling chemical looping combustion technology. CuO is added to the cobalt-based oxygen carrier particles, and the cobalt-based composite oxygen carrier with uniform particle size and fast reaction rate is obtained by sol-gel method.
为了实现上述发明本发明所采用的技术方案是：一种钴基复合载氧体，所述载氧体由Co3O4和CuO组成，其中Co3O4的质量百分数为95%，CuO的质量百分数为5%。In order to realize the above-mentioned invention, the technical scheme adopted by the present invention is: a cobalt-based composite oxygen carrier, the oxygen carrier is composed of Co 3 O 4 and CuO, wherein the mass percentage of Co 3 O 4 is 95%, and the mass percentage of CuO The mass percentage is 5%.
一种钴基复合载氧体的制备方法，包括以下步骤：A preparation method for a cobalt-based composite oxygen carrier, comprising the following steps:
步骤1：将Cu(NO3)2溶液滴加到Co(NO3)2溶液中，搅拌至混合均匀；Step 1: Add the Cu(NO 3 ) 2 solution dropwise into the Co(NO 3 ) 2 solution, and stir until evenly mixed;
步骤2：再加入柠檬酸溶液，70-80℃下边蒸发边搅拌至形成湿凝胶；Step 2: Add citric acid solution, and stir while evaporating at 70-80°C until a wet gel is formed;
步骤3：湿凝胶在干燥温度为105℃下干燥24小时变为干凝胶；Step 3: The wet gel is dried at a drying temperature of 105°C for 24 hours to become a dry gel;
步骤4：将干凝胶置于500℃下煅烧5小时至有机物充分燃烧和硝酸盐完全分解；Step 4: Calcining the xerogel at 500°C for 5 hours until the organic matter is fully burned and the nitrate is completely decomposed;
步骤5：再升温至800℃，活化载氧体，时间为5小时；Step 5: heat up to 800°C to activate the oxygen carrier for 5 hours;
步骤6：将收集到的颗粒研磨、筛分即可得到复合金属氧化物载氧体。Step 6: Grinding and sieving the collected particles to obtain the composite metal oxide oxygen carrier.
步骤1中所述的Co(NO3)2和Cu(NO3)2的质量比为19.5:1。The mass ratio of Co(NO 3 ) 2 and Cu(NO 3 ) 2 in step 1 is 19.5:1.
步骤2中所述的柠檬酸与Co原子的摩尔比为2:1。The molar ratio of citric acid to Co atoms described in step 2 is 2:1.
本发明与现有技术相比的优点在于：The advantage of the present invention compared with prior art is:
1.本发明采用溶胶凝胶法，控制适宜的反应条件，制备出粒径均匀，分散度好的钴基复合载氧体。1. The present invention adopts the sol-gel method, controls suitable reaction conditions, and prepares the cobalt-based composite oxygen carrier with uniform particle size and good dispersion.
2.本发明钴基复合载氧体的制备方法简单，制备出的复合载氧体具有较快的反应速率，释氧速率得到明显提升。2. The preparation method of the cobalt-based composite oxygen carrier of the present invention is simple, and the prepared composite oxygen carrier has a relatively fast reaction rate, and the oxygen release rate is significantly improved.
附图说明Description of drawings
图1为本发明复合载氧体在900℃固定床实验释氧转化率曲线Fig. 1 is the oxygen release conversion rate curve of the composite oxygen carrier of the present invention in a fixed bed experiment at 900°C
具体实施方式Detailed ways
下面结合实例进一步说明本发明：Further illustrate the present invention below in conjunction with example:
本实施例中的原料为分析纯Co(NO3)2·6H2O产品；络合剂为分析纯柠檬酸；掺杂的金属硝酸盐为分析纯Cu(NO3)2·3H2O。The raw material in this example is analytically pure Co(NO 3 ) 2 ·6H 2 O; the complexing agent is analytically pure citric acid; the doped metal nitrate is analytically pure Cu(NO 3 ) 2 ·3H 2 O.
实施例：取29.1gCo(NO3)2·6H2O放入500ml的烧杯中，加入100ml的蒸馏水，然后把烧杯置于带有恒温水浴的磁力搅拌器上，搅拌速度为400rpm。取1.21gCu(NO3)2·3H2O放入100ml的烧杯中，加入50ml的蒸馏水，搅拌至完全溶解。然后把硝酸铜溶液滴加到硝酸钴溶液中，边滴加边搅拌。取42.03g柠檬酸，放入有100ml蒸馏水的烧杯中搅拌至全部溶解，待上述溶液搅拌均匀后，缓慢的加入柠檬酸溶液，边滴加边搅拌。搅拌6个小时后，溶液已经脱水变为粘稠状的湿凝胶。将湿凝胶置于105℃的鼓风干燥箱中，干燥24小时后，烧杯内湿凝胶变为干凝胶。将干凝胶取出，置于500℃的马弗炉中煅烧5小时至柠檬酸和硝酸盐完全分解，再将马弗炉升温至800℃，恒温焙烧5小时，用于活化载氧体，得到复合金属氧化物载氧体，其中Co3O4的含量为95wt.%，CuO的含量为5wt.%。如图1所示，本实施例制备的的钴基复合载氧体释氧速率明显提升。Example: Put 29.1g Co(NO 3 )2·6H 2 O into a 500ml beaker, add 100ml of distilled water, then place the beaker on a magnetic stirrer with a constant temperature water bath, and the stirring speed is 400rpm. Put 1.21g of Cu(NO 3 ) 2 ·3H 2 O into a 100ml beaker, add 50ml of distilled water, and stir until completely dissolved. Then add the copper nitrate solution dropwise into the cobalt nitrate solution, and stir while adding dropwise. Take 42.03g of citric acid, put it into a beaker with 100ml of distilled water and stir until it is completely dissolved. After the above solution is stirred evenly, slowly add the citric acid solution, and stir while adding it dropwise. After stirring for 6 hours, the solution had dehydrated into a viscous wet gel. The wet gel was placed in a blast drying oven at 105° C., and after drying for 24 hours, the wet gel in the beaker became a dry gel. Take out the dry gel, place it in a muffle furnace at 500°C and calcinate it for 5 hours until the citric acid and nitrate are completely decomposed, then raise the temperature of the muffle furnace to 800°C, and roast it at a constant temperature for 5 hours to activate the oxygen carrier to obtain Composite metal oxide oxygen carrier, wherein the content of Co 3 O 4 is 95wt.%, and the content of CuO is 5wt.%. As shown in Figure 1, the oxygen release rate of the cobalt-based composite oxygen carrier prepared in this example is significantly improved.
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Application publication date: 20140514 |