CN1672789A - Catalyst for autothermal reformation of methanol to prepared hydrogen and its prepn process and application - Google Patents
Catalyst for autothermal reformation of methanol to prepared hydrogen and its prepn process and application Download PDFInfo
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Abstract
The catalyst has metal oxide without copper and noble metal as main active component and the composite oxide of RE and transition metal as the catalytic assistant, heat stabilizing assistant, structure stabilizing assistant and active catalyst component support. The addition of the composite oxide of RE and transition metal raises the reaction activity of the catalyst as well as its strength and stability greatly. The preparation process may be co-precipitation one, isometric soaking one or hot decomposition one. In the co-precipitation process or soaking process, adhesive and pore creating agent are added, and the adhesive and pore creating agent is mixture water solution of organic acids, inorganic acids, pseudo-thin diasphore and polymer. The catalyst may be used in hydrogen source system of fuel cell with unstable operation.
Description
Technical Field
The invention relates to a catalyst for autothermal reforming of methanol to produce hydrogen.
The invention also relates to a preparation method of the catalyst.
The invention also relates to the application of the catalyst.
Background
The technical development of Proton Exchange Membrane Fuel Cells (PEMFCs) has been to date, and the problem of fuel cell, i.e. hydrogen source, has become one of the technical bottlenecks hindering commercialization, and has attracted more and more attention and extensive research. The method is characterized in that hydrocarbon such as methanol, gasoline, natural gas and the like is moved in a reforming mode or is prepared on site to be used as a most practical and feasible hydrogen supply mode for a fuel cell to generate electricity, is considered as a first-choice solution of fuel cell hydrogen source technology in the next 10-20 years, research and development work in the field is carried out in many countries in the world at present, multiple research progresses are achieved, multiple fuel cell display vehicles for methanol reforming and gasoline reforming hydrogen sources are provided in the field of fuel cell automobiles, and meanwhile, a large number of companies internationally demonstrate a power generation device integrating fuel reforming and fuel cells.
The on-site hydrogen production of methanol by reforming generally comprises the processes of methanol reforming, CO transformation, CO selective oxidation or pressure swing adsorption to remove CO and the like. The reforming process converts methanol into hydrogen-rich gas, which contains about 5% of CO, and the CO has a poisoning effect on a Pt catalyst of a fuel cell electrode to quickly deactivate the catalyst, so that the CO in the reformed gas is reduced to below 50-100ppm through subsequent reaction processes such as CO water vapor conversion, CO selective oxidation and the like so as to be used for the fuel cell. The methanol reforming process is the most basic and predominant reaction process, with the following major reactions occurring over the catalyst:
wherein, the reaction (1) is a steam reforming process when not existing, and an external heat source is needed for strong endothermic reaction; the presence of reaction (1), referred to as an autothermal reforming or combined reforming hydrogen production process, is a coupling of steam reforming and oxidative reforming processes. In the process of preparing hydrogen by autothermal reforming, a small amount of oxygen (air) is introduced into a methanol and water reaction system to combust part of methanol, the released heat is directly supplied to methanol and water vapor for reforming reaction, and endothermic and exothermic reactions are coupled in situ, so that the requirements of frequent and rapid starting and rapid response when the power is changed of a fuel cell, particularly a vehicle-mounted fuel cell, a boat-used fuel cell or a standby power supply fuel cell, are most probably met.
One of the technical difficulties in the process of preparing hydrogen by auto-thermal reforming of methanol is the development of auto-thermal reforming catalyst of methanol. The catalyst should have a combustion active site and a steam reforming active site at the same time, and the blending of the catalytic active components should ensure the energy balance of the heat absorption and release reaction; at the same time, the catalyst also needs to have high enough activity, stability and strength to meet the special requirements of the fuel cell in unsteady state operation. At present, the reported methanol autothermal reforming hydrogen production catalysts used in the hydrogen source process of fuel cells are mainly divided into two categories, one category is a copper-based catalyst, Cu-Zn-Al is used as a main component, and the purpose of improving the thermal stability and the activity of the catalyst is achieved by adding alkaline earth metal, transition metal oxide or rare earth metal oxide on the basis. Cu-Zn-A1-MOx catalyst as in patent EP1007081A2, wherein the auxiliary agent MOx is one or more of La, Ca, Ga, Cr, Ba, Zr and Ce; and the Cu-Zn-Al-Ce and Cu-Zn-Al-Zr catalysts of patent EP1161992A1, and the like. The catalyst is developed on the basis of a steam reforming catalyst, so that the CO content of reformed gas is low in the process of autothermal reforming of methanol, but the catalyst has the defects of rapid activity attenuation, the heat resistance of the modified catalyst can not meet the requirement of a hydrogen source of a fuel cell, and the catalyst needs to be activated in advance before reaction and needs special passivation treatment when shut down. Another class of catalysts are noble metal catalysts, represented by Pd-Zn catalysts, such as the Pd-Zn-MOx catalyst (MOx is a mixed metal oxide) in patent EP1312413A2, the Pd-Ce-Zn catalyst in patent JP2002282691, the Pd-Zn-Ce-Zr catalyst in patent US2001/0021469A1, the Pd-MOx, Pd-Pt-MOx catalyst in patent JP2001232193, and the like. The heat-resistant stability and the activity of the catalyst are greatly enhanced, the catalyst is more convenient to use than a copper-based catalyst, but the CO content in the reformed gas gradually increases along with the reaction, namely the CO selectivity is poor, and meanwhile, the noble metal has larger consumption and high price. In addition, chinese patents CN1305867 and CN1305868 report a copper-free non-noble metal catalyst, which is used in the methanol autothermal reforming process to obtain higher methanol conversion rate and hydrogen selectivity, but because the catalyst lacks sufficient thermal stabilizing auxiliary agent, structural stabilizing auxiliary agent and support of active component, the catalyst is easy to be pulverized and broken during the use process, so it is difficult to meet the requirements of the fuel cell hydrogen source system, especially the vehicle-mounted hydrogen source system, on catalyst strength and stability during the long-term operation.
Disclosure of Invention
The invention aims to provide a catalyst for hydrogen production by methanol autothermal reforming, which has the advantages of high activity, good strength, good thermal stability, no need of pre-activation in use, no need of special passivation treatment in shutdown, good CO selectivity and relatively low cost, and can meet the special requirements of unsteady operation of a fuel cell system on the catalyst for hydrogen production by methanol autothermal reforming.
It is another object of the present invention to provide a method for preparing the above-mentioned hydrogen catalyst.
The invention provides a methanol autothermal reforming hydrogen production catalyst suitable for a fuel cell hydrogen source system, which takes various defects and deficiencies of the methanol autothermal reforming catalyst in the background technology, takes non-copper-based and non-noble metal composite oxides as main catalytic active components and takes proper rare earth metal and transition metal composite oxide solid solution as a catalytic auxiliary agent according to special requirements of the fuel cell hydrogen source.
The catalyst takes non-copper-based and non-noble metal composite oxides as main active components, and the composite oxides have methanol steam reforming and methanol combustion activities at the same time, so that an endothermic process and an exothermic process are coupled in the same reaction; the rare earth metal and transition metal composite oxide not only serves as a catalytic assistant, but also serves as a thermal stability assistant, a structure stability assistant and a catalyst active component support. The addition of the composite oxide of rare earth metal and transition metal not only improves the reaction activity of the catalyst, but also greatly improves the strength and stability of the catalyst.
The invention relates to a composite oxide catalyst for hydrogen production by autothermal reforming of methanol, which specifically comprises the following components in percentage by weight:
the catalyst takes non-copper-based and non-noble metal composite oxides as main active components of the catalyst, and takes composite oxides of rare earth metals and transition metals as catalytic reaction auxiliary agents, thermal stability auxiliary agents, structure stability auxiliary agents and active component carriers. Wherein the oxide of the auxiliary agent is selected from two or more of rare earth metal lanthanide series such as lanthanum (La), cerium (Ce), gadolinium (Gd), samarium (Sm) and transition metal such as titanium (Ti), chromium (Cr), zirconium (Zr), molybdenum (Mo), vanadium (V), manganese (Mn), nickel (Ni) and the like, the rare earth metal is preferably lanthanum (La), cerium (Ce), and the transition metal is preferably titanium (Ti), zirconium (Zr). The weight of the rare earth metal oxide in the auxiliary agent is not less than 15 percent of the total weight of the auxiliary agent, and preferably 50 to 80 percent. The main active components of the catalyst are selected from two or more oxides of metals 20-30 in the periodic table of elements, such as zinc (Zn), chromium (Cr), iron (Fe) (manganese (Mn), cobalt (Co), nickel (Ni) and vanadium (V), preferably zinc (Zn), chromium (Cr), nickel (Ni) and manganese (Mn), wherein the weight of zinc oxide (ZnO) is not less than 40 percent of the total weight of the active components, preferably 50-80 percent, and the weight of the active components is 15-45 percent of the total weight of the catalyst, preferably 20-30 percent.
The method for preparing the catalyst provided by the invention can use a coprecipitation method, an impregnation method and a thermal decomposition method.
The main catalytic active component is loaded on a prepared catalytic component support body by adopting an equal-volume impregnation method, and the catalytic component support body not only plays a role of a structure stabilizing auxiliary agent and a thermal stabilizing auxiliary agent for a carrier of the catalyst, but also plays a role of improving the activity of the catalyst for a catalytic reaction auxiliary agent. The catalytic component support is prepared by adopting a coprecipitation method or a thermal decomposition method, and the coprecipitation method is preferred. The precursor for preparing the catalytic component support can be selected from soluble nitrates, oxalates or chlorides of rare earth metals and transition metals, and the nitrates are preferred. And drying and roasting the thermal decomposition or coprecipitation product to form the rare earth metal and transition metal composite oxide solid solution. Drying at 80-150 deg.C for 2-8 hr, preferably at 110 deg.C for 4 hr; the roasting temperature and time are 400-800 ℃ for 1-6 hours, preferably 500 ℃ for 2 hours. The prepared composite oxide solid solution powder is crushed to below 200 meshes and is processed and formed by a special process to be used as a catalytic component support body. The operation of the equal-volume impregnation of the main catalytically active component is well known to the person skilled in the art. And drying and roasting the impregnated catalyst to obtain the finished catalyst. The drying temperature and time are 100-150 ℃ for 2-8 hours, preferably 120 ℃ for 4 hours; the roasting temperature and time are 500-900 ℃ for 1-6 hours, preferably 800 ℃ for 2 hours. The impregnation process is repeated one or more times until the desired active ingredient loading is achieved.
The preparation method of the invention can also adopt a thermal decomposition or coprecipitation method to rapidly decompose the precursors of the main catalytic active component and the auxiliary agent to obtain the catalytic component mixed microcrystalline powder, and the catalytic component mixed microcrystalline powder is crushed to be less than 75 mu m and then is processed and molded to prepare the catalyst of the invention. Thermal decomposition is preferred. Drying and roasting the formed catalyst to obtain the finished catalyst. The drying temperature and time are 100-150 ℃ for 2-8 hours, preferably 120 ℃ for 4 hours; the roasting temperature and time are 500-900 ℃ for 1-6 hours, preferably 800 ℃ for 2 hours.
The processing and forming of the preparation method of the invention adopts an extrusion molding or tabletting process, preferably an extrusion molding process. The operation of extrusion or tablet forming processes is well known to those skilled in the art. The forming process is characterized in that peptizing agent is added into catalytic component mixed microcrystalline powder obtained by a thermal decomposition method or a catalytic component support obtained by a coprecipitation method. The addition of the peptizing agent enables the finished catalyst to be kept relativelyHigh activity and high strength. Conventional single binders and pore formers such as pseudo-boehmite (Al)2O3·H2O), polyvinyl alcohol (PVA), polyethylene glycol (PEG), dilute nitric acid and the like can not well meet the requirements of the catalyst on strength and activity. The peptizing agent used by the invention is a certain amount of various organic acids, inorganic acids, pseudo-boehmite and high molecular polymersThe mixture in proportion is water solution. Wherein, the content of the pseudo-boehmite is 1 to 10 percent, the content of the polyvinyl alcohol is 0 to 6 percent, and the content of the organic acid and the inorganic acid is 5 to 25 percent. Preferably 3-6% of pseudo-boehmite, 1-3% of polyvinyl alcohol and 8-15% of organic acid and inorganic acid. The organic acid and the inorganic acid are selected from a mixture of nitric acid, acetic acid and citric acid, wherein the weight ratio of the nitric acid (the concentration is 65 percent) to the acetic acid (the concentration is 36 percent) to the citric acid (solid state) is 1: 1-10: 1-5, and the preferable ratio is 1: 3-8: 2-4.
The invention has the following practical range and application prospect:
the non-copper-based non-noble metal catalyst is used in the process of hydrogen production by methanol autothermal reforming, forms a hydrogen source system together with a CO water vapor conversion process and a COpurification process, and provides a proper hydrogen fuel for a fuel cell, particularly a Proton Exchange Membrane Fuel Cell (PEMFC) system.
Commercialization of fuel cell technology as an efficient and environmentally friendly means of power generation has been increasingly limited by issues with hydrogen sources. The fuel cell has the characteristics of high energy density, high energy conversion efficiency, easy transportation, supplement and storage of liquid fuel and the like, has advantages in the aspects of economy, safety and the like, and can meet the requirements of fuel in the recent or middle period of the fuel cell technology development. Therefore, aiming at the special requirement of the unsteady state operation of the fuel cell, the development of the fossil fuel reforming hydrogen production technology with advanced performance and the related catalyst has important practical significance and wide development prospect. Compared with copper-based methanol autothermal reforming catalysts and noble metal catalysts, the catalyst has high activity, good heat-resistant stability and long service life, does not need to be activated in advance before use, does not need special passivation treatment when shut down midway, and is more suitable for fuel cell hydrogen source systems which are frequently started and carried. The catalyst of the invention lays a good foundation for realizing the technical progress of the hydrogen production by the autothermal reforming of the methanol and further realizing the integration with a fuel cell system in the real sense. Meanwhile, the energy structure of China is mainly coal, methanol can be conveniently and economically prepared from coal, so the energy technology line for realizing power generation from the coal-methanol-fuel cell has special significance for ensuring the energy safety of China.
The novelty and creativity of the invention lie in:
(1) the compositeoxide catalyst has high activity, good heat-resistant stability, good strength and long service life, does not need pre-activation before use, does not need special passivation treatment during shutdown, overcomes the limitations of copper-based catalysts and noble metal catalysts, and is suitable for being applied to fuel cell hydrogen source systems operated in an unsteady state.
(2) In the invention point (1), the catalyst adopts non-copper-based and non-noble metal composite oxides as main active components, the composite oxides have methanol steam reforming and methanol combustion activities at the same time, so that an endothermic process and an exothermic process are coupled in the same reaction, and the selection of the non-copper-based components overcomes the limitations of the conventional copper-based catalyst and noble metal catalyst in the aspects of reaction activity, thermal stability, pre-activation before use, passivation protection after use and the like, so that the catalyst is more suitable for being applied to a fuel cell hydrogen source system.
(3) In the invention point (1), the composite oxide of rare earth metal and transition metal is introduced to form a solid solution skeleton structure, which not only serves as a catalytic assistant, but also serves as a catalyst active component support to play a role of a thermal stability assistant and a structure stability assistant. The addition of the composite oxide of rare earth metal and transition metal not only improves the reaction activity of the catalyst, but also greatly improves the strength and stability of the catalyst.
(4) In the invention point (1), the catalyst forming process is characterized in that the addition of the special formula of the binder and the pore-forming agent ensures that the catalyst not only ensures higher porosity, but also keeps a high-strength framework structure, thereby not only well solving the strength problem of the catalyst, but also ensuring that the catalyst has higher activity.
Drawings
Figure 1 is a stability experiment conducted with the catalyst of example 4.
Figure 2 is a start-stop impact experiment with the catalyst of example 3.
Figure 3 shows the effect of reaction temperature on conversion and reformate gas composition using the catalyst of example 3.
Detailed Description
Example 1: ZnO-Cr prepared by coprecipitation method2O3-CeO2-La2O3-ZrO2Composite oxide catalyst
a) Weighing technical grade Ce (NO)3)3·6H2O90.90 g, technical grade Zr (OH)48.45g，La(NO3)3·6H2O6.35g. Weigh good Zr (OH)4Putting the mixture into a beaker, adding 65-68% concentrated nitric acid, and heating for reaction until no visible particles exist and the solution is transparent. Dissolving Zr (NO)3)4Pouring the solution into the dissolved Ce (NO)3)3And La (NO)3)3And (4) mixing the solution, and filtering for later use.
b) Weighing analytically pure Zn (NO)3)2·6H2O 18.90g，(NH4)2Cr2O7And 5.55g of deionized water is added to dissolve the mixed solution, then the Ce-Zr solution obtained in the step a is mixed with the mixed solution, 25-28% of ammonia water is dripped into the mixed solution by a separating funnel under the condition of continuous stirring, and the ammonia water amount is controlled according to the pH value until the pH value reaches 7-8. The formed Zn-Cr-Ce-Zr coprecipitation is fully stirred, filtered in vacuum,After washing, the mixture is put into an oven to be dried for 15 hours at 110 ℃, and then is put into a muffle furnace to be roasted for 2 hours at 500 ℃. The calcined product was ground to 75 μm or less, and 2.5g of pseudo-boehmite, 0.5ml of 65% nitric acid, 4.0ml of 36% acetic acid, 8g of citric acid and 10m of sulfuric acid were addedDeionized water, mixing thoroughly, extruding with a strip extruder, air drying, and cutting into cylinders of 3 × 4 mm. Putting the cylinder into an oven to dry for 4 hours at 110 ℃, and then putting the cylinder into a muffle furnace to bake for 2 hours at 800 ℃ to obtain ZnO-Cr2O3-CeO2La2O3-ZrO2A composite oxide catalyst (A).
Example 2: ZnO-Cr prepared by dipping method2O3/CeO2Composite oxide catalyst
a) Weighing technical grade Ce (NO)3)3·6H2And adding 90.90g of O, dissolving in deionized water, filtering, and dripping 25-28% of ammonia water into the solution by using a separating funnel, wherein the ammonia water amount is controlled according to the pH value until the pH value reaches 8-9. Formed CeO2And (3) fully stirring, vacuum-filtering, washing, putting into an oven for drying at 110 ℃ for 15 hours, and then putting into a muffle furnace for roasting at 500 ℃ for 2 hours. Grinding the roasted product to below 200 mesh, adding 1.5g of pseudo-boehmite and 1.5ml of 10% nitric acid, mixing thoroughly, extruding into strips with a strip extruder, air drying, and cutting into cylinders of about 3X 4 mm. Putting the cylinder into an oven for drying at 110 ℃ for 4 hours, and then putting the cylinder into a muffle furnace for roasting at 500 ℃ for 2 hours to obtain CeO2And (3) a carrier. The resultant was ground to 12-16 mesh and the water absorption was measured.
b) Weighing analytically pure Zn (NO)3)2·6H2O 18.90g，(NH4)2Cr2O75.55g, adding deionized water to dissolve, setting the volume to be 8ml, and pouring the CeO in the step a2The carrier is dipped in the same volume, the dipped catalyst is put into an oven to be dried for 4 hours at the temperature of 110 ℃, and is roasted for 2 hours at the temperature of 800 ℃ in a muffle furnace to obtain ZnO-Cr2O3/CeO2A composite oxide catalyst (B).
Example 3: ZnO-Cr prepared by thermal decomposition method2O3-CeO2-ZrO2Composite oxide catalyst
a) Weighing technical grade Ce (NO)3)3·6H2O90.90 g, technical grade Zr (OH)48.45g, analytically pure Zn (NO)3)2·6H2O 18.90g，(MH4)2Cr2O75.55g and urea 0.5 g. And (3) fully and uniformly mixing the reagents, putting the reagents into a muffle furnace, carrying out thermal decomposition for 30 minutes at 500 ℃, and quickly cooling to room temperature after the decomposition is finished.
b) Grinding the decomposition product to below 200 mesh, adding 2.5g of pseudo-boehmite, mixing thoroughly, extruding with a plodder, air drying, and cutting into cylinders of about phi 3 × 4 mm. Putting the cylinder into an oven to dry for 4 hours at 110 ℃, and then putting the cylinder into a muffle furnace to bake for 2 hours at 800 ℃ to obtain ZnO-Cr2O3-CeO2-ZrO2A composite oxide catalyst (C).
Example 4: ZnO-Cr prepared by thermal decomposition method2O3-CeO2-ZrO2Composite oxide catalyst
a) The thermal decomposition method for preparing the catalyst microcrystalline powder is the same as that of example 3.
b) 0.5ml of 65% nitric acid, 4.0ml of 36% acetic acid, 8g of citric acid and 10ml of deionized water were added during the catalyst formation, and the rest was performed as in example 3 to obtain ZnO-Cr2O3-CeO2-ZrO2A composite oxide catalyst (D).
Example 5: catalyst evaluation
Grinding the catalyst to 12-16 meshes, and placing in a quartz tube reactor with inner diameter of 18mm at methanol space velocity GHSV of 4000hr-1The methanol conversion rate and the outlet reformed gas composition were measured at a water-alcohol molar ratio of 1.2, an oxygen-alcohol molar ratio of 0.3, a reaction temperature of 530 ℃ and a reaction pressure of normal pressure. The catalyst evaluation results are shown in Table 1.
Comparative examples related to the present invention:
example 6: ZnO/CeO prepared by dipping method2-ZrO2Catalyst and process for preparing same
a) Weighing technical grade Ce (NO)3)3·6H2O90.90 g, technical grade Zr (OH)48.45g。CeO2-ZrO2The coprecipitated support was prepared as in example 1, ground to 12-16 mesh and the water absorption was measured.
b) Weighing analytically pure Zn (NO)3)2·6H218.90g of O, and deionized water is addedDissolving, determining the volume to be 8ml, pouring the carrier obtained in the step a), soaking in the same volume, putting the soaked catalyst into an oven for drying at 110 ℃ for 4 hours, and roasting in a muffle furnace at 800 ℃ for 2 hours to obtain ZnO/CeO2-ZrO2Comparative catalyst example (E).
Example 7: Ru/CeO prepared by dipping method2-ZrO2Noble metal catalyst
a) Weighing technical grade Ce (NO)3)3·6H2O90.90 g, technical grade Zr (OH)48.45g。CeO2-ZrO2The coprecipitated support was prepared as in example 1, ground to 12-16 mesh and the water absorption was measured.
b) Weighing analytically pure RuCl3·3H2O3.5714 g, adding deionized water to dissolve, and setting the volume to 100 ml. Measuring 12ml of the solution, pouring the solution into the carrier obtained in the step a), soaking the carrier in the same volume, putting the soaked catalyst into an oven for drying at 110 ℃ for 4 hours, and roasting the catalyst in a muffle furnace at 800 ℃ for 2 hours to obtain Ru/CeO2-ZrO2Comparative catalyst example (F).
Example 8: ZnO-Cr prepared by thermal decomposition method2O3Catalyst and process for preparing same
a) Weighing analytically pure Zn (NO)3)2·6H2O 18.90g，(NH4)2Cr2O75.55g and urea 0.5 g. And (3) fully and uniformly mixing the reagents, putting the reagents into a muffle furnace, carrying out thermal decomposition for 30 minutes at 500 ℃, and quickly cooling to room temperature after the decomposition is finished.
b) Grinding the decomposition product to below 200 meshes, adding 0.2g of graphite powder, and fully mixingTabletting with a tabletting machine to obtain cylindrical ZnO-Cr with the diameter of about 3 mm by 4mm2O3Comparative catalyst example (G). Comparative catalyst evaluation conditions were the same as in example 5, andthe evaluation results are shown in Table 1.
TABLE 1 evaluation of catalyst Performance
| Sample (I) | Reformed gas composition,% | Initial activity ％ | Life time, hr | |||
| H2 | CO | CO2 | CH4 | |||
| Example 1 | 52.4 | 2.0 | 19.4 | 30ppm | 93.7 | Over 200hr |
| Example 2 | 48.0 | 3.1 | 19.9 | 250ppm | 94.2 | Over 200hr |
| Example 3 | 50.9 | 4.0-4.7 | 18.2 |
| 100 | Over 200hr |
| Example 4 | 51.5 | 2.3-2.6 | 20.5 |
| 100 | Over 200hr |
| Example 6 | 54.6 | 1.1 | 21.3 | 100ppm | 97.1 | Gradual decay of activity |
| Example 7 | 46.5 | 13.4 | 9.2 | 670ppm | 82.3 | - |
| Example 8 | 48.9 | 2.2-2.5 | 19.3 | 30ppm | 85.6 | - |
The invention has the following effects:
1) the catalyst of the invention is used for the reaction of hydrogen production by autothermal reforming of methanol at the methanol space velocity GHSV of 4000hr-1The methanol conversion rate of the reforming reaction is 100% when the molar ratio of water to alcohol is 1.2, the molar ratio of oxygen to alcohol is 0.3, the reaction temperature is 530 ℃, the inlet temperature is 120 ℃, and the reaction pressure is normal pressure; the reformate gas composition is hydrogen (H)2) 51.5% nitrogen (N)2) 25.5%, carbon monoxide (CO) 2.5%, methane (CH)4) Trace amount of carbon dioxide (CO)2)20.5 percent; the hydrogen yield is 1.60NM3H2/kgCH3OH; the methanol conversion rate is maintained above 99.5% after 200 hr. The catalyst has high activity, good CO selectivity and good stability. See fig. 1.
2) The catalyst of the invention can directly carry out the reaction of hydrogen production by autothermal reforming of methanol without pre-reduction and activation, does not need special atmosphere protection during shutdown, does not need special passivation treatment, and keeps the activity and selectivity of the catalyst unchangedafter repeated startup and shutdown impact. See fig. 2, methanol space velocity GHSV 4000hr-1The molar ratio of water to alcohol is 1.2, the molar ratio of oxygen to alcohol is 0.3, the reaction temperature is 530 ℃, the inlet temperature is 120 ℃, and the reaction pressure is normal pressure.
3) The catalyst of the invention can carry out the methanol autothermal reforming hydrogen production reaction within a wide range of the water-alcohol molar ratio of 1.2-1.5, the oxygen-alcohol molar ratio of 0.27-0.31 and the reaction temperature of 470-660 ℃, and the conversion rate of methanol is kept between 90-100 percent, which is particularly important when a hydrogen source system responds to the power change of a fuel cell. The good heat-resisting stability of the catalyst ensures the hydrogen source when the power of the fuel cell changesThe system can still continuously supply qualified product hydrogen. See fig. 3, methanol space velocity GHSV 4000hr-1The molar ratio of water to alcohol is 1.2, the molar ratio of oxygen to alcohol is 0.3, and the reaction pressure is normal pressure.
4) The catalyst is used in a hydrogen source system of a 5 kW-grade methanol autothermal reforming fuel cell, and the space velocity GHSV of methanol is 4000hr-1The molar ratio of water to alcohol is 1.2, the molar ratio of oxygen to alcohol is 0.3, the reaction temperature is 500-.
Claims (14)
1. The catalyst for autothermal reforming of methanol to produce hydrogen consists of composite oxide of RE metal and transition metal as assistant and carrier, and has the structure as shown in the specification:
the weight of the rare earth metal oxide in the auxiliary agent is 15-95% of the total weight of the auxiliary agent;
the active components are two or more than two oxides of metals selected from 20-30 of the periodic table of elements, the weight of the active components accounts for 15-45% of the total weight of the catalyst, and the weight of the zinc oxide accounts for 40-95% of the total weight of the active components.
2. The catalyst of claim 1 wherein the rare earth metal oxide is present in an amount of 50 to 80% by weight of the total promoter.
3. The catalyst of claim 1 wherein the catalytically active component is present in an amount of from 20 to 30% by weight based on the total weight of the catalyst.
4. The catalyst of claim 1 wherein the zinc oxide is present in an amount of 50 to 80% by weight based on the total weight of the active components.
5. The catalyst of claim 1 wherein the rare earth metal is lanthanum, cerium, gadolinium, samarium; the transition metal is titanium, chromium, zirconium, molybdenum, vanadium, manganese and nickel.
6. The catalyst of claim 1 or 5, wherein the rare earth metal is lanthanum, cerium; the transition metal is titanium or zirconium.
7. The catalyst of claim 1 or 4, wherein the catalyst active group is selected from two or more of the oxides of zinc, chromium, iron, manganese, cobalt, nickel, vanadium.
8. The catalyst of claim 1, 4 or 7, wherein the catalyst active group is selected from two or more of the oxides of zinc, chromium, manganese, nickel.
9. A method for preparing the catalyst of claim 1, wherein the coprecipitation method comprises the following main steps:
a) preparing a mixed solution from the auxiliary agent and the active component according to a proportion;
b) adjusting the pH value of the mixed solution to 7-8 by using ammonia water to form a precipitate;
c) filtering, washing the precipitate, drying at 80-150 deg.C for 2-8 hr, and calcining at 400-800 deg.C for 1-6 hr;
d) grinding the roasted product to be less than 75 mu m, adding a binder consisting of organic acid, inorganic acid and pseudo-boehmite or/and a high molecular polymer mixture and a pore-forming agent, and uniformly mixing; wherein, the organic acid and the inorganic acid are the mixture of nitric acid, acetic acid and citric acid, the content is 5-25%, the weight ratio of the nitric acid to the acetic acid to the solid citric acid is 1: 1-10: 1-5, the content of the pseudo-boehmite accounts for 1-10% of the content of the binder and the pore-forming agent, the content of the polyvinyl alcohol is 0-6%, and the rest is deionized water;
e) and d, extruding or pressing the mixed raw materials in the step d, air-drying, drying at the temperature of 100-150 ℃ for 2-8 hours, and roasting at the temperature of 500-900 ℃ for 1-6 hours to obtain the catalyst.
10. A process for the preparation of a catalyst according to claim 1, the impregnation process comprising the main steps of:
a) preparing the auxiliary agent into a mixed solution according to a proportion;
b) adjusting the pH value of the mixed solution to 8-9 by using ammonia water to form a precipitate;
c) filtering, washing the precipitate, drying at 80-150 deg.C for 2-8 hr, and calcining at 400-800 deg.C for 1-6 hr;
d) grinding the roasted product to be less than 75 mu m, adding a binder consisting of organic acid, inorganic acid and pseudo-boehmite or/and a high molecular polymer mixture and a pore-forming agent, and uniformly mixing; wherein, the organic acid and the inorganic acid are the mixture of nitric acid, acetic acid and citric acid, the content is 5-25%, the weight ratio of the nitric acid to the acetic acid to the solid citric acid is 1: 1-10: 1-5, the content of the pseudo-boehmite accounts for 1-10% of the content of the adhesive and the pore-forming agent, the content of the polyvinyl alcohol is 0-6%, and the rest is deionized water.
e) D, extruding or pressing the mixed raw materials in the step d, air-drying, drying at the temperature of 100-;
f) preparing the active components into a solution according to a proportion, and soaking the solution in the same volume of the catalyst carrier;
g) drying the impregnated catalyst carrier at 80-150 ℃ for 2-8 hours, and roasting at 400-800 ℃ for 1-6 hours to obtain the catalyst.
11. A process for preparing the catalyst of claim 1, the main steps of the thermal decomposition process are:
a) weighing solid matters of the auxiliary agent and the active component according to the proportion, and uniformly mixing;
b) thermally decomposing the mixture at 350-600 ℃ for 10-60 minutes, and rapidly cooling to room temperature;
c) grinding the decomposition product to below 200 meshes, adding a binder consisting of organic acid, inorganic acid and pseudo-boehmite or/and a high molecular polymer mixture and a pore-forming agent, and uniformly mixing; wherein, the organic acid and the inorganic acid are the mixture of nitric acid, acetic acid and citric acid, the content is 5-25%, the weight ratio of the nitric acid to the acetic acid to the solid citric acid is 1: 1-10: 1-5, the content of the pseudo-boehmite accounts for 1-10% of the content of the binder and the pore-forming agent, the content of the polyvinyl alcohol is 0-6%, and the rest is deionized water;
d) and c, extruding or pressing the mixed raw materials in the step c, drying at the temperature of 100-150 ℃ for 2-8 hours, and roasting at the temperature of 500-900 ℃ for 1-6 hours to obtain the catalyst.
12. The method according to claim 9, 10 or 11, wherein the binder and pore-forming agent used contain 8-15% of organic and inorganic acids, 3-6% of pseudo-boehmite and 1-3% of polyvinyl alcohol.
13. The method of claim 9, 10 or 11, wherein the binder and pore former are used in a weight ratio of 65% nitric acid to 36% acetic acid to solid citric acid of 1: 3 to 8: 2 to 4.
Use of a catalyst according to any one of the preceding claims in a fuel cell hydrogen source system.
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