CN111573620B - Modularized hydrogen production method - Google Patents
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Abstract
The invention belongs to the technical field of hydrogen production process, and disclosesA modularized hydrogen production method is disclosed, which adopts a CuO-MgO circulating carrier to carry out reaction-regeneration circulation, a methanol reactor takes the water solution of methanol as the raw material, and the high-purity hydrogen is prepared by the synergistic cooperation of the absorption enhancement of the CuO-MgO circulating carrier and the autothermal reforming reaction of chemical chain methanol at the temperature of 200-300 ℃, accompanied by Cu and MgCO 3 Generating; a regeneration reactor, wherein oxygen or air is introduced into the regeneration reactor at 350-450 ℃ to trap high-purity CO 2 Or to obtain CO 2 、N 2 The mixed gas simultaneously realizes the regeneration of the CuO-MgO circulating carrier. The method provided by the invention combines medium-low temperature CuO chemical chain circulation and MgO absorption enhanced reforming, shortens the overall process, and provides a new method and approach for preparing high-purity hydrogen through modular methanol high-efficiency conversion.
Description
Technical Field
The invention belongs to the technical field of hydrogen production processes, and particularly relates to a small modularized hydrogen production method.
Background
With the gradual exhaustion of fossil energy, hydrogen is considered as the most environmentally-friendly 'ultimate energy' in the 21 st century due to the characteristics of high combustion heat value, abundant resources, no pollution of combustion products to the environment and the like, and is concerned by countries in the world. The hydrogen energy has wide application in the fields of fuel cells, hydrogen energy automobiles, aerospace, fine chemical production, food processing, metal smelting and the like, and the percentage of the hydrogen energy in a terminal energy system in China is up to 10% or more. The methanol is used as a carrier of hydrogen energy, has the characteristics of low carbon content, larger energy density, low price and convenient transportation and storage, and becomes an ideal hydrogen energy carrier.
The main catalytic system for the methanol reforming reaction at present is CuO/ZnO/Al 2 O 3 、CuO/CeO 2 /Al 2 O 3 、Cu/Fe/ZrO 2 And the like metal or metal oxide catalysts. However, the temperature required by the catalytic systems for completely converting the methanol is higher, and the higher reaction temperature promotes the cracking reaction of the methanol, so that the generation amount of CO is increased, the purity of hydrogen is reduced, and the hydrogen production process is complicated. The use of noble metal catalysts also leads to a drastic increase in the reaction costs. The existing methanol conversion approaches mainly include methanol steam reforming reaction, partial oxidation reaction of methanol, autothermal reforming reaction of methanol and cracking reaction of methanol. Wherein, the content of CO generated by the methanol cracking reaction is high, and the theoretical hydrogen concentration of the methanol steam reforming reaction can reach 70 vol%But the reaction absorbs heat and cannot be stably operated by self-heating; the hydrogen concentration produced by partial oxidation of methanol and autothermal reforming of methanol is low.
The products of the traditional methanol reforming process are CO and CO 2 And H 2 The fuel is required to be combusted to provide the heat required by the reforming reaction, and the water vapor conversion is required to convert CO into H 2 Then separating CO by acid gas separation device or pressure swing adsorption device 2 The hydrogen purification has long overall flow, high investment and energy consumption, and is not suitable for the miniaturization modularization distribution type hydrogen production. Therefore, it is imperative to provide a new miniaturized methanol utilization technology that can not only solve the above problems, but also meet the future demand for hydrogen energy development.
Disclosure of Invention
The invention aims to provide a modularized hydrogen production method, which adopts a circulating carrier CuO-MgO to absorb and enhance methanol chemical chain autothermal reforming hydrogen production, and realizes partial oxidation of methanol by regulating and controlling lattice oxygen activity and bulk phase migration capacity in CuO; by MgO on CO 2 The absorption effect of the catalyst promotes the balance forward movement of CO water vapor shift reaction, realizes the preparation of the ultra-high purity hydrogen, and can be used for proton exchange membrane fuel cells when the concentration of the generated CO is lower than 50 ppm.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a modular hydrogen production process comprising the steps of:
1) Carrying out reaction-regeneration circulation by adopting a CuO-MgO circulating carrier, preparing a methanol aqueous solution, and preheating the prepared methanol aqueous solution serving as a reactant to obtain a mixed gas of methanol and water vapor;
2) Introducing the mixed gas of the methanol and the steam obtained in the step 1) into a fuel reactor, wherein copper oxide participates in partial oxidation and catalytic reforming reaction of the methanol, and MgO absorbs CO 2 Generation of hydrogen and Cu-MgCO 3 ；
3) Introducing oxygen or air into the regeneration reactor to realize the regeneration of the CuO-MgO circulating carrier and simultaneously capture CO 2 Gas or to obtain CO 2 、N 2 Mixing gas;
the step 2) and the step 3) are circularly reciprocated, so that the autothermal reforming of the methanol based on a chemical chain circulation mode is realized.
Further, the mass ratio of CuO to MgO of the CuO-MgO circulation carrier is 0.06-0.10.
Further, the MgO grain size of the CuO-MgO circulation carrier is 10-100nm.
Further, the molar ratio of water to methanol in the aqueous solution of methanol in the step 1) is 0.3-1.0.
Further, the preheating temperature in the step 1) is 150-200 ℃.
Further, the reaction temperature of the step 2) is 200-300 ℃.
Further, the temperature of the reaction environment in the step 3) is 350-400 ℃.
Further, when the reaction in the step 3) is carried out in an oxygen atmosphere, high purity CO can be trapped 2 A gas; when carried out under an air atmosphere, N is obtained 2 With CO 2 The mixed gas of (1).
The invention has the beneficial effects that:
the modularized hydrogen production method provided by the invention is used for preparing high-purity hydrogen based on the absorption and enhancement of a chemical chain autothermal reforming of methanol by a CuO-MgO circulating carrier. As shown in fig. 1, the method includes a Cu-based chemical looping reforming process and an MgO-based absorption enhanced reforming process, which are organic combinations of the two processes. The Cu-based chemical chain reforming process is shown in figure 2, the copper-based oxygen carrier not only provides lattice oxygen to realize the autothermal reforming reaction of methanol, but also serves as a catalyst to catalyze the methanol conversion, and the main product of the methanol conversion is H 2 And CO 2 . The MgO-based absorption-enhanced reforming process is shown in FIG. 3, in which MgO, as an intermediate temperature absorbent, participates in CO catalytic reforming of methanol 2 The absorption of the CO gas and the promotion of the water-vapor transformation reaction of the CO gas simultaneously, and the final products are all hydrogen, so that the hydrogen with the volume concentration of more than 99 percent can be obtained theoretically.
According to the modularized hydrogen production method disclosed by the invention, as shown in fig. 4, self-heating operation can be realized through CuO-MgO carrier circulation, high-purity hydrogen can be directly prepared, equipment investment such as transformation, gas separation and the like is saved, the flow is greatly shortened, the modularized hydrogen production method can be used for a highly-integrated small-sized distributed methanol hydrogen production device, and the modularized hydrogen production method is suitable for technical layout of a hydrogen feeding station and a vehicle-mounted modularized hydrogen production device.
A relevant reaction model is built by adopting ASPEN Plus software, a Gibbs reactor is adopted as a fuel reactor and a regeneration reactor, and gas waste heat at the outlet of the reactors is used for preheating the aqueous solution of methanol. The calculation result of the ASPEN Plus system shows that the system can realize self-heating operation under the condition of utilizing waste heat, and the heat absorption and release conditions of different reaction processes are analyzed as follows. In the fuel reactor, a methanol vapor reforming reaction, which is an endothermic reaction; magnesium oxide absorbs carbon dioxide and reacts chemically, as an exothermic reaction.
Methanol steam reaction:
CH 3 OH+H2O→CO 2 +3H 2 (1)
CO 2 absorption reaction:
MgO+CO 2 →MgCO 3 (2)
in the regeneration reactor, the reaction of desorbing carbon dioxide by magnesium carbonate is an endothermic reaction; the copper reoxidation reaction is an exothermic reaction. Thus, the system is expected to achieve self-heating balance.
CO 2 And (3) desorption reaction:
MgCO 3 →MgO+CO 2 (3)
and (3) Cu-based oxygen carrier regeneration reaction:
2Cu+O 2 →2CuO (4)
on the premise of meeting the requirements of energy conservation and energy cascade utilization, the regenerative reactor is ensured to be self-heating balance, and meanwhile, the system can meet the self-heating balance, and the heat distribution and H are comprehensively considered 2 The feasible intervals after factors such as concentration and CO concentration are shown in FIG. 5. Therefore, it was initially concluded that the absorption enhanced methanol chemical looping reforming process can achieve system autothermal reforming, yielding high purity hydrogen while CO concentration can be controlled at a lower level.
If oxygen is used as a regeneration medium in the regeneration reactor, high-purity CO can be trapped while regeneration of the circulating carrier is realized 2 A gas. The process is shown as reaction (3) and reaction (4). The process not only can realize the regeneration of MgO-CuO circulating carrier for the next methanol conversion cycle, but also can finally convert carbon in methanol into CO 2 Is collected in the form of (1).
In addition to the above-mentioned methanol steam reforming reaction, partial oxidation reaction of methanol, cracking reaction of methanol and autothermal reforming of methanol, the present patent proposes a novel chemical chain methanol reforming process using lattice oxygen [ O ] in CuO] 2 As oxygen source, the autothermal reaction of methanol is carried out, the reaction process being as follows:
CH 3 OH+[O] 2- →CO 2 +2H 2 (5)
drawings
FIG. 1 is a CO capture in a modular hydrogen production process provided by the present invention 2 A process schematic;
FIG. 2 is a chemical looping diagram of a Cu-based oxygen carrier in a modular hydrogen production method provided by the invention;
FIG. 3 is a diagram of a Mg-based absorber absorption enhancement cycle in a modular hydrogen production process provided by the present invention;
FIG. 4 is a schematic diagram of CO capture in a modular hydrogen production process provided by the present invention 2 A method flow diagram;
FIG. 5 Overall consideration of Heat distribution, H 2 Feasible intervals after factors such as concentration, CO concentration and the like;
FIG. 6 shows different MgO/CH 3 OH and CuO/CH 3 Hydrogen concentration profile at OH molar ratio;
FIG. 7 different MgO/CH 3 OH and CuO/CH 3 Hydrogen atom utilization efficiency distribution diagram under OH molar ratio;
FIG. 8 different MgO/CH 3 OH and CuO/CH 3 A CO concentration distribution diagram under an OH molar ratio;
FIG. 9 shows different MgO/CH 3 OH and CuO/CH 3 A methanol conversion rate distribution diagram under the OH molar ratio;
FIG. 10H per methanol flow Rate 2 A graph of the yield with the temperature variation;
FIG. 11 is a graph showing the variation of CO concentration and H atom utilization efficiency with temperature per unit methanol flow rate;
FIG. 12 different H 2 O/CH 3 OH molar ratio of H 2 Yield, CO concentration and H atom utilization efficiency distribution maps;
FIG. 13 different H 2 O/CH 3 Fuel reactor and regeneration reactor heat profiles at OH molar ratios.
Detailed Description
Example 1:
1) Preparing a methanol aqueous solution with the water-alcohol ratio of 0.5, and preheating the methanol aqueous solution as a reactant to a mixed gas of methanol and water vapor with the temperature of 150 ℃;
2) And introducing the preheated mixed gas of the methanol and the water vapor into a fuel reactor with the temperature of 300 ℃, wherein the mass ratio of the CuO to the MgO is 0.06. Copper oxide participates in partial oxidation and catalytic reforming reaction of methanol, mgO participates in absorption enhancement reaction in the methanol conversion process, and a CuO-MgO circulating carrier finally generates Cu-MgCO 3 ；
3) Introducing oxygen into a regeneration reactor at the temperature of 420 ℃ to realize the regeneration of the CuO-MgO circulating carrier and simultaneously trap CO 2 A gas;
4) The above steps are repeated in a circulating way, and the autothermal reforming of the methanol based on a chemical chain circulation mode is realized.
Example 2:
1) Preparing a methanol aqueous solution with the water-alcohol ratio of 0.3, and preheating the methanol aqueous solution as a reactant to be a mixed gas of methanol and water vapor with the temperature of 180 ℃;
2) And (3) introducing the preheated mixed gas of the methanol and the water vapor into a fuel reactor at the temperature of 200 ℃, wherein the mass ratio of the CuO to the MgO is 0.08. Copper oxide participates in partial oxidation and catalytic reforming reaction of methanol, mgO participates in absorption enhancement reaction in the methanol conversion process, and a CuO-MgO circulating carrier finally generates Cu-MgCO 3 ；
3) Introducing air into a regeneration reactor with the temperature of 450 ℃ to realize the regeneration of the CuO-MgO circulating carrier and obtain CO 2 、N 2 Mixing gas;
4) The above steps are repeated in a circulating way, and the autothermal reforming of the methanol based on a chemical chain circulation mode is realized.
Example 3:
1) Preparing a methanol aqueous solution with the water-alcohol ratio of 0.6, and preheating the methanol aqueous solution as a reactant to a mixed gas of methanol and water vapor with the temperature of 200 ℃;
2) And introducing the preheated mixed gas of the methanol and the steam into a fuel reactor with the temperature of 220 ℃, wherein the mass ratio of the CuO to the MgO is 0.07. The copper oxide participates in partial oxidation and catalytic reforming reaction of methanol, the MgO participates in absorption enhancement reaction in the methanol conversion process, and the CuO-MgO circulating carrier finally generates Cu-MgCO 3 ；
3) Introducing air into a regeneration reactor with the temperature of 350 ℃ to realize the regeneration of the CuO-MgO circulating carrier and obtain CO 2 、N 2 Mixing gas;
4) The above steps are repeated in a circulating way, and the autothermal reforming of the methanol based on a chemical chain circulation mode is realized.
Example 4:
1) Preparing a methanol aqueous solution with the water-alcohol ratio of 1.0, and preheating the methanol aqueous solution as a reactant to form a mixed gas of methanol and water vapor with the temperature of 160 ℃;
2) And (3) introducing the preheated mixed gas of the methanol and the water vapor into a fuel reactor at the temperature of 240 ℃, wherein the mass ratio of the CuO to the MgO is 0.10. Copper oxide participates in partial oxidation and catalytic reforming reaction of methanol, mgO participates in absorption enhancement reaction in the methanol conversion process, and a CuO-MgO circulating carrier finally generates Cu-MgCO 3 ；
3) Introducing oxygen into a regeneration reactor with the temperature of 380 ℃ to realize the regeneration of the CuO-MgO circulating carrier and simultaneously trap CO 2 A gas;
4) The above steps are repeated in a circulating way, and the autothermal reforming of the methanol based on a chemical chain circulation mode is realized.
Respectively explore different MgO/CH 3 OH and CuO/CH 3 The hydrogen gas concentration, hydrogen atom utilization efficiency, carbon monoxide gas concentration, and methanol conversion ratio at the OH molar ratio were calculated and shown in fig. 6, 7, 8, and 9, respectively. In the result of hydrogen concentration distributionAdherence of MgO/CH 3 The OH molar ratio is increased, the hydrogen concentration is obviously improved, and MgO/CH 3 When the OH molar ratio reaches about 1, the hydrogen concentration can reach 99 percent. With MgO/CH 3 The OH molar ratio continues to increase and the theoretical hydrogen concentration can be higher. The efficiency of H atom utilization is defined as the H in the product 2 The ratio of the number of H atoms of (A) to the number of H atoms supplied as a reaction raw material, as shown in FIG. 7, follows CuO/CH 3 The improvement of the OH molar ratio linearly decreases the efficiency of H atom utilization. This is because as the flow rate of CuO increases, more H atoms are converted into water, resulting in a decrease in the utilization efficiency of hydrogen atoms, cuO/CH 3 When the OH molar ratio is 0.7, the utilization efficiency of H atoms is about 70 percent; the analysis result of the CO concentration distribution shows that the CuO/CH is high 3 OH molar ratio and high MgO/CH 3 The conversion of CO is facilitated under the condition of OH molar ratio, and the MgO/CH is low 3 OH molar ratio and low CuO/CH 3 The CO concentration under the OH molar ratio can reach more than 0.5 percent, and the operation interval is avoided; explore different CuO/CH 3 OH and MgO/CH 3 The influence of the OH molar ratio on the conversion rate of the methanol can be found out that the conversion rate of the methanol tends to be completely converted at the temperature of 220 ℃, and the conversion rate of the methanol can reach more than 99 percent.
Optimizing the above-mentioned MgO/CH 3 OH and CuO/CH 3 The effect of different temperatures on hydrogen yield, CO concentration and H atom utilization efficiency was investigated using ASPEN Plus software under OH molar ratio conditions, and the results are shown in fig. 10 and 11. It was found that temperature has less influence on the yield of hydrogen and that relatively high yields of hydrogen can be obtained also at low temperatures. This is because the final reactions due to the enhanced absorption are all in the direction of hydrogen generation, and thus although the temperatures are different, the theoretical yields of hydrogen generated are very close. Further, as shown in FIG. 11, the CO concentration is rather increased by the high temperature, that is, the cracking reaction of methanol occurs. Explores different H under the chemical chain methanol conversion method 2 O/CH 3 OH to H 2 The results of the production rate, the efficiency of H atom utilization, the CO concentration, and the system energy balance are shown in fig. 12 and 13. High H 2 O/CH 3 The OH molar ratio is favorable for improving the hydrogen yield and reducing the CO concentration, but the energy required by the system is increasedAnd the hydrogen atom utilization efficiency is lowered, so that there is a relatively superior H 2 O/CH 3 The OH molar ratio range is 0.3-1.0, the system comprehensive performance is ensured to be optimal, and compared with the traditional methanol steam reforming technology, the catalyst has lower H 2 O/CH 3 The OH molar ratio saves a water-vapor conversion and acid gas separation device in the traditional process, shortens the flow, and is more favorable for system energy conservation and miniaturization hydrogen production. Therefore, in this example, under the conditions of a water-alcohol ratio of 0.5 and a methanol conversion temperature of 300 ℃, the CO concentration was 0.2295% and the H atom utilization efficiency was 60.587%. The embodiment can realize the autothermal reforming of methanol to prepare high-purity hydrogen and realize the cyclic regeneration of the circulating carrier of CuO-MgO.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (8)
1. A modularized hydrogen production method is characterized in that a CuO-MgO circulating carrier is adopted for reaction-regeneration circulation; the method comprises the following steps:
1) Preparing an aqueous solution of methanol, and preheating the aqueous solution of the methanol as a reactant to obtain a mixed gas of the methanol and water vapor;
2) Introducing the mixed gas of the methanol and the steam obtained in the step 1) into a fuel reactor, wherein copper oxide participates in partial oxidation and catalytic reforming reaction of the methanol, and MgO absorbs CO 2 Generation of hydrogen and Cu-MgCO 3 ；
3) Introducing oxygen or air into the regeneration reactor to realize the regeneration of the CuO-MgO circulating carrier and simultaneously capture CO 2 Gas or obtaining CO 2 、N 2 Mixing gas;
the step 2) and the step 3) are circularly reciprocated, so that the autothermal reforming of the methanol based on a chemical chain circulation mode is realized.
2. The modular hydrogen production method according to claim 1, wherein the mass ratio of CuO to MgO of the CuO-MgO circulating carrier is 0.06-0.10.
3. The modular hydrogen production method of claim 1, wherein the circulating support of CuO-MgO has an MgO grain size of 10-100nm.
4. The modular hydrogen production method according to claim 1, wherein the molar ratio of water to methanol in the aqueous solution of methanol in step 1) is 0.3-1.0.
5. The modular hydrogen production method according to claim 1, characterized in that the preheating temperature in step 1) is 150-200 ℃.
6. The modular hydrogen production method according to claim 1, characterized in that the reaction temperature of step 2) is 200-300 ℃.
7. The modular hydrogen production method according to claim 1, characterized in that the reaction environment temperature of step 3) is 350-400 ℃.
8. The modular hydrogen production method according to claim 1, wherein the reaction in step 3) is performed in an oxygen atmosphere, so that high purity CO can be captured 2 A gas; when carried out under an air atmosphere, N is obtained 2 With CO 2 The mixed gas of (1).
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