CN107804824A - A kind of compound calcium iron oxygen carrier and its hydrogen production of chemical chain cooperate with CO2Capture method - Google Patents
A kind of compound calcium iron oxygen carrier and its hydrogen production of chemical chain cooperate with CO2Capture method Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 103
- 239000001257 hydrogen Substances 0.000 title claims abstract description 100
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000000126 substance Substances 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 26
- MMAFLWPTWXNMQO-UHFFFAOYSA-N [Ca]O[Fe] Chemical compound [Ca]O[Fe] MMAFLWPTWXNMQO-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 148
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000001301 oxygen Substances 0.000 claims abstract description 108
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 108
- 239000011575 calcium Substances 0.000 claims abstract description 58
- 238000006722 reduction reaction Methods 0.000 claims abstract description 50
- 230000009467 reduction Effects 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 33
- 239000000446 fuel Substances 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 230000002195 synergetic effect Effects 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 239000000969 carrier Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000002309 gasification Methods 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005243 fluidization Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 19
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 239000000292 calcium oxide Substances 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000006479 redox reaction Methods 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000002485 combustion reaction Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000008021 deposition Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910001567 cementite Inorganic materials 0.000 description 5
- 238000011946 reduction process Methods 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
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Abstract
本发明公开了一种复合型钙铁载氧体及其化学链制氢协同CO2捕集方法，将Ca2Fe2O5作为化学链制氢载氧体，复合型钙铁载氧体通过两步氧化‑还原反应即可实现化学链制氢并协同CO2气体捕集，相应的反应器只由燃料反应器与蒸汽反应器即可实现化学链制氢。燃料还原阶段，Ca2Fe2O5被还原生成单质Fe与CaO同时可分离并捕集CO2气体；水蒸气氧化阶段，单质Fe、CaO与水蒸气反应，一步生成Ca2Fe2O5并得到高纯度氢气，如此循环往复即可完成基于新型钙铁载氧体下的两步化学链制氢循环。循环过程中，载氧体可一步从Fe0被氧化为Fe3+，与传统的Fe2O3作为载氧体相比，在加入铁的摩尔量相同的情况下，可产生更多的氢气。同时，该化学链制氢方法从载氧体抗磨损及能耗等方面也具有较大优势。
The invention discloses a composite calcium iron oxygen carrier and its chemical chain hydrogen production synergistic CO 2 capture method. Ca 2 Fe 2 O 5 is used as the chemical chain hydrogen production oxygen carrier, and the composite calcium iron oxygen carrier passes through The two-step oxidation-reduction reaction can realize chemical chain hydrogen production and cooperate with CO2 gas capture, and the corresponding reactor can realize chemical chain hydrogen production only by fuel reactor and steam reactor. In the fuel reduction stage, Ca 2 Fe 2 O 5 is reduced to form elemental Fe and CaO, which can simultaneously separate and capture CO 2 gas; in the water vapor oxidation stage, elemental Fe, CaO and water vapor react to form Ca 2 Fe 2 O 5 and High-purity hydrogen is obtained, and the two-step chemical chain hydrogen production cycle based on the new calcium-iron oxygen carrier can be completed by repeating this cycle. During the cycle, the oxygen carrier can be oxidized from Fe 0 to Fe 3+ in one step. Compared with the traditional Fe 2 O 3 as the oxygen carrier, more hydrogen can be produced under the same molar amount of iron added. . At the same time, the chemical chain hydrogen production method also has great advantages in terms of oxygen carrier wear resistance and energy consumption.
Description
技术领域technical field
本发明涉及一种复合型钙铁载氧体及其化学链制氢协同CO2捕集方法，属于燃烧化工技术领域。The invention relates to a composite calcium-iron oxygen carrier and its chemical chain hydrogen production and CO2 capture method, belonging to the technical field of combustion chemical industry.
背景技术Background technique
化学链燃烧技术是将传统的燃料与空气或氧气直接燃烧，借助于载氧体在两个反应器的氧化与还原，燃料与空气在不接触的条件下，由载氧体将氧传递到燃料中进行燃烧。化学链燃烧作为一种新型的能源利用形式与技术，具有燃料转化率高、二氧化碳分离与捕集以及低污染物排放等优势。而化学链制氢技术，是基于化学链燃烧的基础上提出的一种高效环保制氢方式。相比该技术，传统的蒸汽重整技术能量转化效率较低需要消耗化石能源且其技术路线较为复杂。采用化学链制氢技术不仅能够制备得到高纯度的氢气，同时可实现系统内部分离并捕集CO2气体。The chemical looping combustion technology is to directly burn the traditional fuel with air or oxygen, with the help of the oxidation and reduction of the oxygen carrier in the two reactors, the fuel and the air are not in contact, and the oxygen is transferred to the fuel by the oxygen carrier. burn in. As a new form and technology of energy utilization, chemical looping combustion has the advantages of high fuel conversion rate, carbon dioxide separation and capture, and low pollutant emissions. The chemical chain hydrogen production technology is an efficient and environmentally friendly hydrogen production method based on chemical chain combustion. Compared with this technology, the energy conversion efficiency of traditional steam reforming technology is low, it needs to consume fossil energy and its technical route is more complicated. The chemical chain hydrogen production technology can not only produce high-purity hydrogen, but also realize the internal separation of the system and capture CO2 gas.
氢能作为一种清洁高效的二次能源，其燃烧效率高、产物清洁无污染。氢能的用途也是十分广泛，在能源电力、化工合成等社会各行各业中都扮演着不可替代的作用。传统的化学链制氢技术，由燃料反应器、蒸汽反应器和空气反应器组成，由Fe2O3或改性后的Fe2O3作为载氧体，经过燃料反应器被还原为Fe或FeO、蒸汽反应器被氧化为Fe3O4以及空气反应器被进一步氧化为Fe2O3，从而实现铁基载氧体的三步还原与氧化，以及铁基载氧体下的化学链制氢协同CO2捕集。化学链制氢过程中，通过载氧体在三个反应器，蒸汽反应器、燃料反应器与空气反应器的氧化与还原，实现制备高浓度氢气的同时捕集CO2气体。作为氧与能量的载体，使用高性能的载氧体是化学链制氢技术的核心。国内外的学者已对Ni、Cu、Fe、Mn等金属氧化物作为载氧体的性能及其热力学性能、抗烧结性能进行了探究，发现以铁基载氧体相对其他的载氧体具有明显的优势。As a clean and efficient secondary energy source, hydrogen energy has high combustion efficiency and clean and pollution-free products. Hydrogen energy is also widely used, playing an irreplaceable role in all walks of life such as energy, electricity, and chemical synthesis. The traditional chemical chain hydrogen production technology consists of a fuel reactor, a steam reactor and an air reactor. Fe 2 O 3 or modified Fe 2 O 3 is used as an oxygen carrier, which is reduced to Fe or FeO, the steam reactor is oxidized to Fe 3 O 4 and the air reactor is further oxidized to Fe 2 O 3 , thus realizing the three-step reduction and oxidation of the iron-based oxygen carrier, and the chemical chain formation under the iron-based oxygen carrier Hydrogen synergistically captures CO2 . In the process of chemical chain hydrogen production, through the oxidation and reduction of oxygen carrier in three reactors, steam reactor, fuel reactor and air reactor, CO2 gas can be captured while producing high-concentration hydrogen. As the carrier of oxygen and energy, the use of high-performance oxygen carrier is the core of chemical chain hydrogen production technology. Scholars at home and abroad have explored the properties of Ni, Cu, Fe, Mn and other metal oxides as oxygen carriers, their thermodynamic properties, and anti-sintering properties, and found that iron-based oxygen carriers have obvious advantages compared with other oxygen carriers. The advantages.
然而，采用单一的氧化铁作为载氧体，其循环稳定性能较差经过多次氧化还原制氢后，会出现严重的表面的烧结与孔堵塞，严重的影响了制氢的效果。且水蒸气气化阶段，Fe只能由零价被水蒸气氧化到Fe3O4状态，需要经过燃烧阶段，才能使Fe回到Fe3+状态。采用不同的制备方法如浸渍法、共沉淀法、离子交换法以及溶胶凝胶法使得Fe2O3与其他惰性载体如Al2O3、ZrO2、TiO2、CeO2、MgAl2O4等并可以一定程度上的提高载氧体的活性或稳定性，但对Fe被水蒸气氧化过程中的氧化程度并没有所提高。基于以上探究，提出一种低成本、高效率的新型化学链制氢的载氧体，是化学链制氢技术发展的关键。However, using a single iron oxide as an oxygen carrier has poor cycle stability. After repeated redox hydrogen production, severe surface sintering and pore blockage will occur, which seriously affects the hydrogen production effect. And in the steam gasification stage, Fe can only be oxidized by water vapor from zero to the Fe 3 O 4 state, and it needs to go through the combustion stage to return Fe to the Fe 3+ state. Using different preparation methods such as impregnation method, co-precipitation method, ion exchange method and sol-gel method to make Fe 2 O 3 and other inert supports such as Al 2 O 3 , ZrO 2 , TiO 2 , CeO 2 , MgAl 2 O 4 etc. And it can improve the activity or stability of the oxygen carrier to a certain extent, but it does not improve the oxidation degree of Fe in the process of oxidation by water vapor. Based on the above research, proposing a low-cost, high-efficiency new oxygen carrier for chemical looping hydrogen production is the key to the development of chemical looping hydrogen production technology.
发明内容Contents of the invention
技术问题：本发明提供一种复合型钙铁载氧体及其化学链制氢协同CO2捕集方法，提出将Ca2Fe2O5作为化学链制氢的载氧体，该方法可替代传统的三步法化学链制氢，通过燃料还原与水蒸气气化两步即可实现化学链制氢，同时捕集CO2气体。该载氧体循环稳定性能好，铁的化合价利用率高，载氧体在流化床循环中的反应磨损可有大幅度减小。Technical problem: The present invention provides a composite calcium-iron oxygen carrier and its chemical chain hydrogen production synergistic CO 2 capture method, and proposes to use Ca 2 Fe 2 O 5 as an oxygen carrier for chemical chain hydrogen production. This method can replace The traditional three-step chemical chain hydrogen production can realize chemical chain hydrogen production through two steps of fuel reduction and water vapor gasification, and capture CO2 gas at the same time. The oxygen carrier has good circulation stability, high valence utilization rate of iron, and the reaction wear of the oxygen carrier in fluidized bed circulation can be greatly reduced.
技术方案：本发明的复合型钙铁载氧体及其化学链制氢协同CO2捕集方法，包括如下步骤：Technical solution: The composite calcium-iron oxygen carrier and its chemical chain hydrogen production synergistic CO2 capture method of the present invention comprise the following steps:
1)采用Ca2Fe2O5作为载氧体，将CO、CH4、合成气中的任一种作为还原剂，在燃料反应器中于850-950℃下进行载氧体还原反应，还原得到Fe与CaO状态，同时捕集载氧体还原反应产生的CO2；1) Ca 2 Fe 2 O 5 is used as the oxygen carrier, and any one of CO, CH 4 , and synthesis gas is used as the reducing agent, and the oxygen carrier reduction reaction is carried out at 850-950°C in the fuel reactor, and the reduction Obtain the state of Fe and CaO, and simultaneously capture CO 2 produced by the reduction reaction of the oxygen carrier;
2)将经过还原后的Fe与CaO送入蒸汽反应器作为载氧体，在850-950℃温度下，与作为氧化剂的水蒸气进行载氧体氧化反应，得到Ca2Fe2O5，同时捕集载氧体氧化反应产生的高浓度氢气，并将得到的Ca2Fe2O5返回输送至燃料反应器。2) Send the reduced Fe and CaO into a steam reactor as an oxygen carrier, and carry out an oxygen carrier oxidation reaction with water vapor as an oxidant at a temperature of 850-950°C to obtain Ca 2 Fe 2 O 5 , and at the same time The high-concentration hydrogen gas produced by the oxygen carrier oxidation reaction is captured, and the resulting Ca 2 Fe 2 O 5 is returned to the fuel reactor.
本发明方法的优选方案中，步骤1)中合成气为CO、H2、CH4和CO2中的两种或多种的混合。In a preferred version of the method of the present invention, the synthesis gas in step 1) is a mixture of two or more of CO, H 2 , CH 4 and CO 2 .
本发明方法的优选方案中，步骤1)中的合成气为以下任一种：煤气化生成的气体、煤热解生成的气体、生物质气化生成的气体、生物质热解后生成的气体，气体主要成分均包括H2、CO、CH4和CO2。In the preferred version of the method of the present invention, the synthesis gas in step 1) is any of the following: gas generated by coal gasification, gas generated by coal pyrolysis, gas generated by biomass gasification, gas generated after biomass pyrolysis , the main gas components include H 2 , CO, CH 4 and CO 2 .
本发明方法的优选方案中，燃料反应器和蒸汽反应器均采用流化床反应器。In the preferred version of the method of the present invention, both the fuel reactor and the steam reactor are fluidized bed reactors.
本化学链制氢协同CO2捕集方法的优选方案中，步骤1)与步骤2)所用燃料反应器与蒸汽反应器均为流化床反应器。In the preferred scheme of the chemical looping hydrogen production synergistic CO2 capture method, the fuel reactor and the steam reactor used in step 1) and step 2) are all fluidized bed reactors.
有益效果：本发明与现有技术相比，具有以下优点：Beneficial effect: compared with the prior art, the present invention has the following advantages:
1)本发明提出采用Ca2Fe2O5作为化学链制氢的载氧体，用于化学链制氢协同CO2捕集。Ca2Fe2O5载氧体被还原过程中，不出发中间价态的转变，即可直接被还原为CaO与Fe。在保证还原速率的同时，避免了还原过程中的大量积碳。1) The present invention proposes to use Ca 2 Fe 2 O 5 as an oxygen carrier for chemical looping hydrogen production, which is used for chemical looping hydrogen production and CO 2 capture. During the reduction process of the Ca 2 Fe 2 O 5 oxygen carrier, it can be directly reduced to CaO and Fe without changing the intermediate valence state. While ensuring the reduction rate, a large amount of carbon deposition in the reduction process is avoided.
2)Ca2Fe2O5催化剂作为化学链制氢或化学链燃烧的载氧体，具有较好的载氧能力，无论CO还是CH4作为还原剂，均具有较好的稳定性能，且采用CO作为还原剂的还原阶段，其积碳量较少，循环稳定性较强。载氧体氧化还原阶段转化率稳定、反应性强，是两步化学链制氢技术的前景载氧体。2) The Ca 2 Fe 2 O 5 catalyst, as an oxygen carrier for chemical looping hydrogen production or chemical looping combustion, has a good oxygen carrying capacity, whether CO or CH 4 is used as a reducing agent, it has good stability. In the reduction stage of CO as the reducing agent, the amount of carbon deposition is less and the cycle stability is stronger. The oxygen carrier has a stable conversion rate and strong reactivity in the redox stage, and is a promising oxygen carrier for the two-step chemical chain hydrogen production technology.
3)本发明方法采用Ca2Fe2O5作为化学链制氢载氧体，与传统Fe2O3及其改性载氧体相比较，Fe0可一步被氧化为Fe3+，因此可以省去传统化学链制氢中的空气反应器。载氧体只需经过燃料反应器还原与蒸汽反应器氧化两步，即可实现化学链制氢协同CO2捕集，且其制氢量在相同铁摩尔数且在还原阶段被完全还原的情况下，氢气产量可提高12.5％。且由于省去了空气反应器，该化学链制氢工艺的成本大大降低，相同循环次数下载氧体在反应器中的磨损程度也有大幅度降低、且减小反应器可使整个反应循环的能量损耗降低。3) The method of the present invention uses Ca 2 Fe 2 O 5 as the oxygen carrier for chemical chain hydrogen production. Compared with the traditional Fe 2 O 3 and its modified oxygen carrier, Fe 0 can be oxidized to Fe 3+ in one step, so it can The air reactor in the traditional chemical chain hydrogen production is omitted. The oxygen carrier only needs to go through two steps of fuel reactor reduction and steam reactor oxidation to realize chemical chain hydrogen production and CO2 capture, and the hydrogen production amount is the same as the number of iron moles and is completely reduced in the reduction stage. Under this condition, the hydrogen production can be increased by 12.5%. And because the air reactor is omitted, the cost of the chemical chain hydrogen production process is greatly reduced, the wear degree of the oxygen body in the reactor is also greatly reduced under the same number of cycles, and the reduction of the reactor can make the energy of the entire reaction cycle Loss reduction.
附图说明Description of drawings
图1为Ca2Fe2O5催化剂H2-TPR实验结果；Figure 1 shows the experimental results of Ca 2 Fe 2 O 5 catalyst H 2 -TPR;
图2为CO作为还原剂不同载氧体(Ca2Fe2O5与Fe2O3)被还原性能对比；Figure 2 is a comparison of the reduction performance of CO as a reducing agent with different oxygen carriers (Ca 2 Fe 2 O 5 and Fe 2 O 3 );
图3为不同还原时间载氧体XRD实验结果；Figure 3 is the XRD experimental results of oxygen carriers with different reduction times;
图4为CO作为还原剂不同浓度CO(5％，10％，20％，30％)对Ca2Fe2O5载氧体还原阶段的影响；Figure 4 is the effect of CO as a reducing agent with different concentrations of CO (5%, 10%, 20%, 30%) on the reduction stage of Ca 2 Fe 2 O 5 oxygen carriers;
图5为CO作为还原剂不同温度(800℃，850℃，900℃，950℃)对Ca2Fe2O5载氧体还原阶段的影响；Figure 5 shows the effect of CO as a reducing agent at different temperatures (800°C, 850°C, 900°C, 950°C) on the reduction stage of Ca 2 Fe 2 O 5 oxygen carrier;
图6为CH4作为还原剂不同载氧体(Ca2Fe2O5与Fe2O3)被还原性能对比；Figure 6 is a comparison of the reduction performance of different oxygen carriers (Ca 2 Fe 2 O 5 and Fe 2 O 3 ) using CH 4 as a reducing agent;
图7为不同还原剂(CO与CH4)对Ca2Fe2O5载氧体还原阶段的影响；Figure 7 shows the effect of different reducing agents (CO and CH 4 ) on the reduction stage of Ca 2 Fe 2 O 5 oxygen carrier;
图8为化学链燃烧10次CO还原与O2氧化循环实验；Figure 8 shows 10 cycles of CO reduction and O2 oxidation experiments in chemical looping combustion;
图9为化学链燃烧10次CH4还原与O2氧化循环实验；Figure 9 is a 10-time CH4 reduction and O2 oxidation cycle experiment of chemical looping combustion;
图10为化学链制氢20次CO还原与H2O氧化循环实验；Figure 10 shows 20 cycles of CO reduction and H 2 O oxidation experiments for chemical looping hydrogen production;
图11为化学链制氢过程中10次循环氢气浓度；Figure 11 shows the hydrogen concentration in 10 cycles during the chemical looping hydrogen production process;
图12为化学链制氢过程中20次循环载氧体转化率；Figure 12 is the conversion rate of oxygen carrier in 20 cycles in the process of chemical looping hydrogen production;
图13为20次化学链制氢还原阶段Ca2Fe2O5载氧体转化率；Figure 13 shows the conversion rate of Ca 2 Fe 2 O 5 oxygen carrier in the reduction stage of 20 chemical looping hydrogen production;
图14为20次化学链制氢氧化阶段CaO+Fe载氧体转化率；Figure 14 is the conversion rate of CaO+Fe oxygen carrier in the 20 chemical looping hydrogen oxidation stages;
图15为不同还原阶段与循环次数下载氧体XRD实验结果；Fig. 15 is the XRD experiment results of different reduction stages and cycle times of the oxygen body;
图16为复合型钙铁载氧体Ca2Fe2O5两步法化学链制氢协同CO2气体捕集示意图。Fig. 16 is a schematic diagram of the two-step chemical looping hydrogen production and CO 2 gas capture by the composite calcium iron oxygen carrier Ca 2 Fe 2 O 5 .
具体实施方式Detailed ways
下面结合实施例和说明书附图对本发明作进一步的说明。The present invention will be further described below in conjunction with embodiment and accompanying drawing.
实施例1：Example 1:
包括以下步骤：Include the following steps:
1)采用Ca2Fe2O5作为载氧体，CO作为还原剂，在850℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2气体；1) Ca 2 Fe 2 O 5 is used as the oxygen carrier, CO is used as the reducing agent, and the oxygen carrier is reduced to the state of Fe and CaO in the fuel reactor at 850°C, and CO 2 gas is captured at the same time;
2)经过还原后的Fe与CaO经过蒸汽反应器，在900℃下与燃料反应器中，被水蒸气氧化一步生成Ca2Fe2O5，同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor, and are oxidized by water vapor in a fuel reactor at 900°C to generate Ca 2 Fe 2 O 5 and high-concentration hydrogen at the same time. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
实施例2Example 2
1)采用Ca2Fe2O5作为载氧体，CH4作为还原剂，在880℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2；1) Ca 2 Fe 2 O 5 is used as the oxygen carrier, CH 4 is used as the reducing agent, and the oxygen carrier is reduced to the state of Fe and CaO in the fuel reactor at 880°C, and CO 2 is captured at the same time;
2)经过还原后的Fe与CaO经过蒸汽反应器，在920℃温度下，被水蒸气氧化后，一步生成Ca2Fe2O5同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor and are oxidized by water vapor at a temperature of 920°C to generate Ca 2 Fe 2 O 5 in one step and simultaneously generate high-concentration hydrogen. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
实施例3Example 3
1)采用Ca2Fe2O5作为载氧体，H2、CO与CH4合成气作为还原剂，在950℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2；1) Using Ca 2 Fe 2 O 5 as the oxygen carrier, H 2 , CO and CH 4 synthesis gas as the reducing agent, the oxygen carrier is reduced to the state of Fe and CaO in the fuel reactor at 950°C, and the Collect CO 2 ;
2)经过还原后的Fe与CaO经过蒸汽反应器，在950℃温度下，被水蒸气氧化后，一步生成Ca2Fe2O5同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor and are oxidized by water vapor at a temperature of 950°C to generate Ca 2 Fe 2 O 5 in one step and simultaneously generate high-concentration hydrogen. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
实施例4Example 4
1)采用Ca2Fe2O5作为载氧体，CO与CH4合成气作为还原剂，在880℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2；1) Ca 2 Fe 2 O 5 is used as the oxygen carrier, CO and CH 4 syngas are used as the reducing agent, and the oxygen carrier is reduced to the state of Fe and CaO in the fuel reactor at 880°C, and CO 2 is captured at the same time ;
2)经过还原后的Fe与CaO经过蒸汽反应器，在900℃温度下，被水蒸气氧化后，一步生成Ca2Fe2O5同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor and are oxidized by water vapor at a temperature of 900°C to generate Ca 2 Fe 2 O 5 in one step and simultaneously generate high-concentration hydrogen. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
实施例5Example 5
1)采用Ca2Fe2O5作为载氧体，CO与H2合成气作为还原剂，在920℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2；1) Using Ca 2 Fe 2 O 5 as the oxygen carrier, CO and H 2 synthesis gas as the reducing agent, and reducing the oxygen carrier to Fe and CaO in the fuel reactor at 920°C, while capturing CO 2 ;
2)经过还原后的Fe与CaO经过蒸汽反应器，在920℃温度下，被水蒸气氧化后，一步生成Ca2Fe2O5同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor and are oxidized by water vapor at a temperature of 920°C to generate Ca 2 Fe 2 O 5 in one step and simultaneously generate high-concentration hydrogen. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
实施例6Example 6
1)采用Ca2Fe2O5作为载氧体，CH4与H2作为还原剂，在890℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2；1) Ca 2 Fe 2 O 5 is used as the oxygen carrier, CH 4 and H 2 are used as the reducing agent, and the oxygen carrier is reduced to the state of Fe and CaO in the fuel reactor at 890°C, and CO 2 is captured at the same time;
2)经过还原后的Fe与CaO经过蒸汽反应器，在950℃温度下，被水蒸气氧化后，一步生成Ca2Fe2O5同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor and are oxidized by water vapor at a temperature of 950°C to generate Ca 2 Fe 2 O 5 in one step and simultaneously generate high-concentration hydrogen. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
实施例7Example 7
1)采用Ca2Fe2O5作为载氧体，煤气化后的气体作为还原剂，在875℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2；1) Ca 2 Fe 2 O 5 is used as the oxygen carrier, the gas after coal gasification is used as the reducing agent, and the oxygen carrier is reduced to the state of Fe and CaO in the fuel reactor at 875°C, and CO 2 is captured at the same time;
2)经过还原后的Fe与CaO经过蒸汽反应器，在850℃温度下，被水蒸气氧化后，一步生成Ca2Fe2O5同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor and are oxidized by water vapor at a temperature of 850°C to generate Ca 2 Fe 2 O 5 in one step and simultaneously generate high-concentration hydrogen. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
实施例8Example 8
1)采用Ca2Fe2O5作为载氧体，煤热解后的气体作为还原剂，在875℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2；1) Ca 2 Fe 2 O 5 is used as the oxygen carrier, and the gas after coal pyrolysis is used as the reducing agent, and the oxygen carrier is reduced to the state of Fe and CaO in the fuel reactor at 875°C, and CO 2 is captured at the same time ;
2)经过还原后的Fe与CaO经过蒸汽反应器，在850℃温度下，被水蒸气氧化后，一步生成Ca2Fe2O5同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor and are oxidized by water vapor at a temperature of 850°C to generate Ca 2 Fe 2 O 5 in one step and simultaneously generate high-concentration hydrogen. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
实施例9Example 9
1)采用Ca2Fe2O5作为载氧体，生物质气化后的气体作为还原剂，在875℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2；1) Ca 2 Fe 2 O 5 is used as the oxygen carrier, and the gas after biomass gasification is used as the reducing agent, and the oxygen carrier is reduced to the state of Fe and CaO in the fuel reactor at 875°C, and CO is captured at the same time 2 ;
2)经过还原后的Fe与CaO经过蒸汽反应器，在925℃温度下，被水蒸气氧化后，一步生成Ca2Fe2O5同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor and are oxidized by water vapor at a temperature of 925°C to generate Ca 2 Fe 2 O 5 in one step and simultaneously generate high-concentration hydrogen. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
实施例10Example 10
1)采用Ca2Fe2O5作为载氧体，生物质热解后的气体作为还原剂，在875℃下与燃料反应器中，将载氧体还原为Fe与CaO状态，同时捕集CO2；1) Ca 2 Fe 2 O 5 is used as the oxygen carrier, and the gas after biomass pyrolysis is used as the reducing agent, and the oxygen carrier is reduced to the state of Fe and CaO in the fuel reactor at 875°C, and CO is captured at the same time 2 ;
2)经过还原后的Fe与CaO经过蒸汽反应器，在925℃温度下，被水蒸气氧化后，一步生成Ca2Fe2O5同时产生高浓度氢气。如此往复，从而实现两步法化学链制氢循环协同CO2捕集。2) The reduced Fe and CaO pass through a steam reactor and are oxidized by water vapor at a temperature of 925°C to generate Ca 2 Fe 2 O 5 in one step and simultaneously generate high-concentration hydrogen. Reciprocating in this way, the two-step chemical looping hydrogen production cycle and CO2 capture are realized.
本发明提出采用Ca2Fe2O5作为化学链制氢的载氧体，用于化学链制氢协同CO2捕集。图1为Ca2Fe2O5载氧体的H2-TPR图，根据TPR实验结果可知，Ca2Fe2O5倾向于一步被还原成Fe与CaO。而采用Fe2O3作为载氧体时，需要经过Fe2O3→Fe3O4→FeO→Fe多步还原后，才能够得到用于制氢的Fe。图2为Fe2O3与Ca2Fe2O5还原性能对比图，由图可知，在还原阶段的前半阶段，氧化铁与Ca2Fe2O5具有几乎相同的反应性能，随着时间的增加，Ca2Fe2O5的反应性能明显高于Fe2O3，在相同时间内，其被还原程度有明显的提高。根据以上分析，以CO作为还原剂为例，分别列出了两种不同载氧体被还原过程的化学反应方程式：The present invention proposes to use Ca 2 Fe 2 O 5 as an oxygen carrier for chemical chain hydrogen production, which is used for chemical chain hydrogen production and CO 2 capture. Figure 1 is the H 2 -TPR diagram of the Ca 2 Fe 2 O 5 oxygen carrier. According to the TPR experimental results, it can be known that Ca 2 Fe 2 O 5 tends to be reduced to Fe and CaO in one step. However, when Fe 2 O 3 is used as the oxygen carrier, Fe for hydrogen production can only be obtained after multi-step reduction of Fe 2 O 3 →Fe 3 O 4 →FeO →Fe. Figure 2 is a comparison chart of the reduction performance of Fe 2 O 3 and Ca 2 Fe 2 O 5. It can be seen from the figure that in the first half of the reduction stage, iron oxide and Ca 2 Fe 2 O 5 have almost the same reaction performance. increase, the reactivity of Ca 2 Fe 2 O 5 is significantly higher than that of Fe 2 O 3 , and its reduction degree is significantly improved in the same time. According to the above analysis, taking CO as the reducing agent as an example, the chemical reaction equations of the reduction process of two different oxygen carriers are listed respectively:
Fe2O3作为载氧体被CO还原： Fe2O3 is reduced by CO as an oxygen carrier:
Ca2Fe2O5作为载氧体被CO还原：Ca 2 Fe 2 O 5 is reduced by CO as an oxygen carrier:
图3所示为同意阶段、不同还原时间下的XRD结果，可以发现，还原时间为5分钟、10分钟、与20分钟时，存在在物质主要为未反应的Ca2Fe2O5以及与CO还原后生成的CaO与Fe。该结果可进一步证明，Ca2Fe2O5载氧体被还原过程中，不出发中间价态的转变，即可直接被还原为CaO与Fe。此外，对不同影响因素下载氧体被还原性能展开了探究，结果如图4-7，分别代表不同CO浓度、不同还原温度、不同载氧体下甲烷还原性能以及Ca2Fe2O5载氧体下，不同还原剂对其还原性能的影响。通过对不同因素影响的考察，找出了最适宜的操作条件与工况，在保证还原速率的同时，避免了还原过程中的大量积碳。Figure 3 shows the XRD results of the same stage and different reduction times. It can be found that when the reduction time is 5 minutes, 10 minutes, and 20 minutes, the substances present are mainly unreacted Ca 2 Fe 2 O 5 and CO CaO and Fe formed after reduction. This result can further prove that the Ca 2 Fe 2 O 5 oxygen carrier can be directly reduced to CaO and Fe without changing the intermediate valence state during the reduction process. In addition, the reduction performance of the oxygen carrier under different influence factors was explored. The results are shown in Figure 4-7, respectively representing different CO concentrations, different reduction temperatures, methane reduction performance under different oxygen carriers and Ca 2 Fe 2 O 5 oxygen carrier In vitro, the effect of different reducing agents on its reducing performance. Through the investigation of the influence of different factors, the most suitable operating conditions and working conditions have been found out, which can avoid a large amount of carbon deposition in the reduction process while ensuring the reduction rate.
Ca2Fe2O5催化剂作为化学链制氢或化学链燃烧的载氧体，具有较好的载氧能力。如图8、9所示，分别为采用CO还原+O2氧化与CH4还原+O2氧化的十次化学链燃烧实验。可以看到，采用Ca2Fe2O5作为载氧体，无论CO还是CH4作为还原剂，均具有较好的稳定性能，且根据热重的实验数据可知，采用CO作为还原剂的还原阶段，其积碳量较少，循环稳定性较强。而采用CH4作为还原剂的还原阶段，当Ca2Fe2O5被还原完全或接近被还原完全时，其质量增长较为严重，当质量增长到一定程度后，又逐渐趋于稳定。该部分质量增长是由于碳化铁的生成导致的。采用Fe2O3作为载氧体时，碳化铁生成的反应方程式为：Ca 2 Fe 2 O 5 catalyst, as an oxygen carrier for chemical looping hydrogen production or chemical looping combustion, has a good oxygen carrying capacity. As shown in Figures 8 and 9, there are ten chemical looping combustion experiments using CO reduction + O 2 oxidation and CH 4 reduction + O 2 oxidation, respectively. It can be seen that when Ca 2 Fe 2 O 5 is used as the oxygen carrier, no matter CO or CH 4 is used as the reducing agent, they all have good stability. , with less carbon deposition and stronger cycle stability. In the reduction stage using CH 4 as the reducing agent, when Ca 2 Fe 2 O 5 is completely reduced or nearly completely reduced, the mass increase is serious, and when the mass increases to a certain extent, it gradually tends to be stable. This part of the mass increase is due to the formation of iron carbide. When Fe 2 O 3 is used as the oxygen carrier, the reaction equation for the formation of iron carbide is:
生成的碳化铁，在氧化阶段与H2O反应，又生成Fe3O4：The generated iron carbide reacts with H 2 O in the oxidation stage to generate Fe 3 O 4 :
Ca2Fe2O5作为载氧体、CO作为还原剂时，经过CO长时间的还原后的载氧体质量有所增加，而XRD结果中并未检测到Fe3C的存在，因此该部分质量增加是由于CO气体的歧化反应产生CO2气体与C，并进一步在载氧体上积碳造成的。载氧体在还原后部分阶段，载氧体几乎被完全还原，丧失了氧化性，导致CO发生歧化反应。然而，该部分积碳量很少，且通过确定载氧体的反应活性调整相应的还原剂浓度与反应时间，可有效控制或避免积碳的发生。而采用CH4作为还原剂时，XRD实验结果证实了碳化铁的生成。生成的碳化铁在氧化阶段与水蒸气或O2发生反应，生成未饱和价态的Fe离子，其在CaO存在的条件下，又可继续被氧化，最终生成Ca2Fe2O5，即三价铁状态。When Ca 2 Fe 2 O 5 was used as the oxygen carrier and CO was used as the reducing agent, the mass of the oxygen carrier increased after CO was reduced for a long time, but the presence of Fe 3 C was not detected in the XRD results, so this part The mass increase is due to the disproportionation reaction of CO gas to produce CO gas and C, and further carbon deposition on the oxygen carrier. In some stages after the reduction of the oxygen carrier, the oxygen carrier is almost completely reduced and loses its oxidative properties, leading to the disproportionation reaction of CO. However, the amount of carbon deposition in this part is very small, and by determining the reactivity of the oxygen carrier and adjusting the corresponding reducing agent concentration and reaction time, the occurrence of carbon deposition can be effectively controlled or avoided. When CH 4 was used as the reducing agent, the XRD experimental results confirmed the formation of iron carbide. The generated iron carbide reacts with water vapor or O 2 in the oxidation stage to generate Fe ions in an unsaturated valence state, which can be further oxidized in the presence of CaO to finally generate Ca 2 Fe 2 O 5 , that is, three Iron state.
如图10所示，为热重下采用CO气体作为还原剂，水蒸气作为氧化剂的20次两步化学链制氢实验结果图。该图充分的证明了该复合型钙铁载氧体的化学链制氢协同CO2捕集方法。经过20次循环CO还原与H2O氧化反应后，载氧体仍保持相当良好的稳定性。如图11所示，采用固定床作为化学链制氢反应器，新型钙铁催化剂作为载氧体的10次化学链制氢实验结果。氢气的平均浓度维持在99％以上。催化剂采用柠檬酸高温发泡法制备得到，催化剂本身具有一定的积碳与碳酸钙，因此在第一次制氢阶段，积碳会与水蒸气发生反应生成一定量的CO气体影响氢气的浓度：As shown in Fig. 10, it is the results of 20 two-step chemical chain hydrogen production experiments using CO gas as the reducing agent and water vapor as the oxidizing agent under thermogravimetric conditions. This figure fully demonstrates the chemical chain hydrogen production synergistic CO2 capture method of this composite calcium iron oxygen carrier. After 20 cycles of CO reduction and H2O oxidation, the oxygen carrier still maintains a fairly good stability. As shown in Figure 11, the results of 10 chemical looping hydrogen production experiments using the fixed bed as the chemical looping hydrogen production reactor and the new calcium-iron catalyst as the oxygen carrier. The average concentration of hydrogen is maintained above 99%. The catalyst is prepared by citric acid high-temperature foaming method. The catalyst itself has certain carbon deposits and calcium carbonate. Therefore, in the first hydrogen production stage, carbon deposits will react with water vapor to generate a certain amount of CO gas, which affects the concentration of hydrogen:
图12-14分别为采用热重作为化学链制氢反应器下载氧体20次氧化还原转化率、还原阶段不同时间下载氧体转化率以及氧化阶段载氧体转化率统计。根据实验结果可知，载氧体20次氧化还原阶段转化率稳定、反应性强，是两步化学链制氢技术的前景载氧体。Figures 12-14 respectively show the 20 redox conversion rates of the oxygen carrier in the chemical looping hydrogen production reactor, the conversion rate of the oxygen carrier at different times in the reduction stage, and the statistics of the oxygen carrier conversion rate in the oxidation stage. According to the experimental results, the oxygen carrier has a stable conversion rate and strong reactivity in the 20 redox stages, and is a promising oxygen carrier for the two-step chemical chain hydrogen production technology.
传统的化学链制氢技术，由Fe2O3或改性后的Fe2O3作为载氧体，经过燃料反应器被还原为Fe或FeO、蒸汽反应器被氧化为Fe3O4以及空气反应器被进一步氧化为Fe2O3，实现铁基载氧体的三步还原与氧化，以及铁基载氧体下的化学链制氢协同CO2捕集。本发明的复合型钙铁载氧体及其化学链制氢协同CO2捕集方法，提出采用Ca2Fe2O5作为化学链制氢载氧体，与传统Fe2O3及其改性载氧体相比较，Fe0可一步被氧化为Fe3+，因此可以省去传统化学链制氢中的空气反应器。载氧体只需经过燃料反应器还原与蒸汽反应器氧化两步，即可实现化学链制氢协同CO2捕集，且其制氢量在相同铁摩尔数且在还原阶段被完全还原的情况下，氢气产量可提高12.5％。且由于省去了空气反应器，该化学链制氢工艺的成本大大降低，相同循环次数下载氧体在反应器中的磨损程度也有大幅度降低、且减小反应器可使整个反应循环的能量损耗降低。两种化学链制氢方法的净反应方程式如下：The traditional chemical chain hydrogen production technology uses Fe 2 O 3 or modified Fe 2 O 3 as an oxygen carrier, which is reduced to Fe or FeO in a fuel reactor, oxidized to Fe 3 O 4 in a steam reactor, and air The reactor is further oxidized to Fe 2 O 3 to realize the three-step reduction and oxidation of iron-based oxygen carrier, and the chemical chain hydrogen production under the iron-based oxygen carrier to cooperate with CO 2 capture. The composite calcium iron oxygen carrier and its chemical chain hydrogen production synergistic CO 2 capture method of the present invention proposes to use Ca 2 Fe 2 O 5 as the chemical chain hydrogen production oxygen carrier, and the traditional Fe 2 O 3 and its modification Compared with oxygen carrier, Fe 0 can be oxidized to Fe 3+ in one step, so the air reactor in traditional chemical chain hydrogen production can be omitted. The oxygen carrier only needs to go through two steps of fuel reactor reduction and steam reactor oxidation to realize chemical chain hydrogen production and CO2 capture, and the hydrogen production amount is the same as the number of iron moles and is completely reduced in the reduction stage. Under this condition, the hydrogen production can be increased by 12.5%. And because the air reactor is omitted, the cost of the chemical chain hydrogen production process is greatly reduced, the wear degree of the oxygen body in the reactor is also greatly reduced under the same number of cycles, and the reduction of the reactor can make the energy of the entire reaction cycle Loss reduction. The net reaction equations of the two chemical looping hydrogen production methods are as follows:
传统三步化学链制氢：Traditional three-step chemical chain hydrogen production:
CO+8/9H2O+1/18O2→CO2+8/9H2 (公式8)CO+8/9H 2 O+1/18O 2 →CO 2 +8/9H 2 (Formula 8)
新型两步化学链制氢：New two-step chemical chain hydrogen production:
CO+H2O→CO2+H2 (公式9)CO+H 2 O→CO 2 +H 2 (Equation 9)
由此可见，传统化学链制氢，有一部分燃料用于燃烧提供系统热量，而本发明所提出的新型化学链制氢方法中，燃料与水直接反应制氢，产物均为目标产物，在燃料反应器生成的CO2被捕集的同时，蒸汽反应器产生高浓度H2。It can be seen that in the traditional chemical chain hydrogen production, a part of the fuel is used for combustion to provide system heat, but in the new chemical chain hydrogen production method proposed by the present invention, the fuel and water directly react to produce hydrogen, and the products are all target products. While the CO 2 produced by the reactor is captured, the steam reactor produces a high concentration of H 2 .
上述实施例仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和等同替换，这些对本发明权利要求进行改进和等同替换后的技术方案，均落入本发明的保护范围。The foregoing embodiments are only preferred implementations of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principles of the present invention, several improvements and equivalent replacements can be made, which are important to the rights of the present invention. Technical solutions requiring improvement and equivalent replacement all fall within the protection scope of the present invention.
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| CN116946972A (en) * | 2023-06-19 | 2023-10-27 | 中国科学院广州能源研究所 | A device and method for pyrolysis of organic solid waste coupled with chemical chain hydrogen production and simultaneous carbon capture |
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