CN116177491B - Microwave-driven methanol reforming rapid hydrogen production method - Google Patents
Microwave-driven methanol reforming rapid hydrogen production method Download PDFInfo
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Abstract
The invention discloses a method for quickly producing hydrogen by microwave-driven methanol reforming, which comprises the steps that raw materials of a methanol/water mixed solution can be directly pumped into a tubular microwave reactor preloaded with a catalyst, the catalyst bed is quickly heated to the working temperature under the radiation of microwaves, and the raw materials of the methanol/water mixed solution are quickly reformed into a catalyst mainly containing H under the action of the catalyst 2 And CO 2 Is a mixed gas of (1); condensing a small amount of methanol and water which are not completely converted after cooling the mixed gas, collecting and storing the obtained mixed condensate of the methanol and the water, and recycling the mixed condensate of the methanol and the water into a raw material tank to be reused as a raw material; meanwhile, the mixed gas is primarily dried, and then the mixed gas is deeply dried, and CO is removed 2 Obtaining high-purity H 2 And (5) a product. The invention uses microwave as energy source to drive methanol/water to reform into the main H-containing catalyst on high-efficiency catalyst 2 /CO 2 The content of impurity gas in the reformed gas flow is stably kept below 0.3mol percent, the reaction is rapid, and the catalytic efficiency is high.
Description
Technical Field
The invention relates to a methanol reforming hydrogen production technology, in particular to a microwave-driven methanol reforming rapid hydrogen production method, and belongs to the field of energy and chemical industry.
Background
H 2 As a secondary energy source and hydrogenation raw material with wide sources and environmental protection, the catalyst has wide application in the fields of transportation, energy source, industry and the like. However, the application scenes of hydrogen are different, and the applicable hydrogen production methods are also different, for example, the traditional hydrogen production process mainly comprises natural gas hydrogen production, coal hydrogen production, water electrolysis hydrogen production and the like. Compared with the traditional hydrogen production method, the methanol and water reforming hydrogen production process has the advantages of rich raw materials, safety, easy storage and transportation and the like, and has strong application scene adaptability. Meanwhile, methanol is used as a hydrogen carrier to be catalytically reformed with water to generate H 2 And CO 2 The hydrogen production method is simple in process and high in integration of deviceAnd the miniaturization is characterized by supplying high-purity H for hydrogen fuel cell automobiles in the transportation field 2 The potential scheme can break through the bottleneck problems of high equipment requirement, high safety risk, small hydrogen storage amount and the like when the hydrogen fuel cell vehicle adopts the high-pressure gas cylinder storage scheme.
High purity H supply for hydrogen fuel cell car by reforming methanol and water 2 In the example of a point-of-use hydrogen scenario, efficient reforming of methanol and water to H is not required 2 With CO 2 In addition, it is also desirable that the reforming reaction be rapidly started and stopped. Therefore, such on-demand hydrogen demands are more demanding in terms of the response speed of the methanol catalytic reforming reaction system. The whole heating process of the traditional thermocatalytic reaction is slow, the heat utilization efficiency is low, and the application requirement of instant hydrogen utilization cannot be met. CN104157889a discloses a reactor for producing hydrogen by reforming methanol and steam for fuel cell automobiles, which adopts a technical scheme of microwave irradiation to heat reactants, and compared with the traditional heating, microwaves are instantaneously and directly transmitted to catalyst particles in the reactor in the form of electromagnetic waves, and local high temperature is generated at active sites where the catalytic reaction really occurs to drive chemical reaction, so that the reaction temperature can be greatly reduced, and the energy utilization efficiency is greatly improved. However, in the scheme, the methanol and the aqueous solution are required to be evaporated into steam through an evaporator and then enter a catalyst for reaction, so that the energy consumption is increased, and the ceramic alumina carrier and the catalyst in the reactor have weak microwave absorption capability and unsatisfactory catalytic effect.
In addition, conventional thermocatalytic methanol and water reforming typically employs CuO/ZnO based catalysts that require H at 350-500℃ 2 The pre-reduction in the methanol or the methanol/water mixed gas flow for a plurality of hours has complicated process, increases the maintenance complexity of a reaction system and is not friendly to the scene of using hydrogen immediately.
Disclosure of Invention
The invention aims to provide a method for quickly producing hydrogen by reforming methanol under microwave drive, raw materials can directly enter a catalyst for reaction in a liquid state, and the catalyst has high catalytic efficiency and high reaction speed.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a microwave-driven methanol reforming rapid hydrogen production method comprises the following steps:
directly pumping the raw material of the methanol/water mixed solution in the liquid storage tank A into a tubular microwave reactor preloaded with a catalyst, wherein the molar ratio of water/methanol is 1.01-1.5;
under the microwave radiation, the catalyst bed layer is quickly heated to the working temperature of 180-320 ℃, and the methanol/water mixed raw material is quickly reformed into the main H-containing material under the action of the catalyst 2 And CO 2 The catalyst is prepared from CuO/ZnO composite oxide active component and microwave absorption component, wherein the microwave absorption component is silicon carbide and manganese oxide (MnO) x ) One or more of manganese-cerium composite oxides;
the mixed gas is cooled and then condensed with a small amount of methanol and water which are not completely converted, and the obtained mixed condensate of methanol and water is collected, stored and circulated into a liquid storage tank A to be reused as a raw material;
at the same time mainly contain H 2 And CO 2 The mixture gas is primarily dried, then the mixture gas is deeply dried by a deep drying unit, and the mixture gas after the deep drying is further subjected to CO 2 Removing to obtain H 2 And (5) a product.
As a further preferable aspect of the present invention, the liquid storage tank a is further mixed with peroxide to prepare a methanol/water/peroxide mixed raw material; or storing the peroxide in a liquid storage tank B, and respectively pumping and mixing the methanol/water mixed raw material and the peroxide into a tubular microwave reactor.
As a further preferred aspect of the present invention, the peroxide is one or more of hydrogen peroxide, peracetic acid, and peroxyformic acid, and the content of the total peroxide in the methanol/water/peroxide mixed raw material is controlled to be 0.1 to 3wt.%, preferably 0.5 to 2wt.%.
As a further preferred aspect of the present invention, the catalyst is obtained by mechanically mixing a CuO/ZnO composite oxide active component and a microwave absorbing component; the mass ratio of the CuO/ZnO composite oxide active component to the microwave absorbing component is 0.8-2.5, preferably 1-1.75.
As a further preferred aspect of the present invention, the catalyst is obtained by supporting a CuO/ZnO composite oxide active component on the surface of a microwave absorbing component; the mass ratio of the CuO/ZnO composite oxide active component to the microwave absorbing component is 0.6-2, preferably 1.2-1.5.
As a further preferred aspect of the present invention, the molar ratio of Cu to Zn in the CuO/ZnO composite oxide active ingredient is 1.5 to 4; more preferably, the molar ratio of Cu to Zn is 2 to 3.2.
As a further preferred aspect of the present invention, the preparation process of the CuO/ZnO composite oxide active component is as follows: mixing copper precursor and zinc precursor with corresponding Cu/Zn molar ratio, adding citric acid monohydrate in 0.2-1 times of the precursor mixture, adding distilled water in 0.5-5 times of the total mixture, mixing homogeneously at 100-160 deg.c, evaporating to dry, and final calcining in air at 450-600 deg.c for 1-3 hr.
As a further preferred aspect of the present invention, the loading method is: mixing copper precursor and zinc precursor with corresponding Cu/Zn molar ratio, adding citric acid monohydrate in 0.5-1.5 times of the precursor mixture, adding distilled water in 4-10 times of the total mixture mass to dissolve to form transparent solution, adding microwave absorbing component into the transparent solution, evaporating water to form viscous mixed slurry under stirring condition, and calcining in 500-650 deg.c for 1-3 hr.
As a further preferred aspect of the present invention, the copper precursor is one or more of copper nitrate and its hydrate, copper acetate and its hydrate; the zinc precursor is one or more of zinc nitrate and hydrate thereof, zinc acetate and hydrate thereof, zinc chloride and hydrate thereof, and zinc hydroxide.
As a further preferable aspect of the present invention, the radiation power density of the microwaves is controlled to be 20 to 400kW/m during the reaction 3 Preferably 50 to 200kW/m 3 。
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses microwaves as energy sources to drive methanol/water to reform on the efficient catalystContaining H 2 /CO 2 Can realize CO and CH in reforming gas stream 4 Excellent results in that the content of the impurity gas is stably maintained at 0.3mol.% or less;
(2) In the microwave-driven methanol/water reforming hydrogen production process, the catalyst does not need to be pre-reduced. Under microwave radiation, methanol/water raw materials are pumped in to realize rapid in-situ reduction of the catalyst, and the catalyst state is rapidly self-regulated to a high-activity state and stably works. Compared with the traditional thermocatalytic process, the method omits a hydrogen pre-reduction process for a plurality of hours, can realize the rapid start of hydrogen production by reforming methanol, can save at least 60% of hydrogen production start time, and promotes the realization of the methanol/water hydrogen production process to be used immediately after starting;
(3) The methanol/water reforming hydrogen production is driven by microwaves, electrification of the hydrogen production process can be realized, feasibility of integration, miniaturization and intelligent control of a hydrogen production system is improved, and capability of the methanol/water reforming hydrogen production process for adapting to complex application scenes is enhanced.
Drawings
FIG. 1 is a schematic diagram of a microwave reforming reaction system according to embodiment 1 of the present invention;
FIG. 2 is a schematic diagram of a microwave reforming reaction system according to embodiment 2 of the present invention;
FIG. 3 is a schematic diagram of a microwave reforming reaction system according to embodiment 3 of the present invention;
FIG. 4 is a schematic diagram of a microwave reforming reaction system according to embodiment 4 of the present invention;
in FIGS. 1 to 4, 1-liquid storage tank A, 2-transfer pump A, 3-pipeline heating vaporizer, 4-microwave reactor, 5-cooler, 6-deep drying unit, 7-CO 2 The device comprises a removal unit, an 8-liquid storage tank B, a 9-delivery pump B and a 10-mixer;
FIG. 5 shows the composition of the microwave methanol reformate at various temperatures in example 5 of the present invention.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
Example 1
The present invention provides a microwave reforming with potential for highly integrated miniaturization of devicesThe reaction system, as shown in FIG. 1, comprises a liquid storage tank A1, a delivery pump A2, a microwave reactor 4, a cooler 5, a deep drying unit 6 and CO 2 The removal unit 7 stores mixed solution raw materials in a liquid storage tank A, the liquid storage tank A1 is connected with a feed inlet of the microwave reactor 4 through a delivery pump A2, a catalyst bed is filled in the microwave reactor 4, an air outlet of the microwave reactor 4 is connected with a cooler 5, a liquid outlet of the cooler 5 is connected with the liquid storage tank A1, an air outlet of the cooler 5 is connected with an air inlet end of the deep drying unit 6, and an air outlet end of the deep drying unit 6 is connected with CO 2 A removal unit 7.
The methanol/water mixed solution or the raw material of the methanol/water/peroxide mixed solution in the liquid storage tank A1 is directly pumped into a tubular microwave reactor 4 preloaded with a catalyst through a delivery pump A2, and the molar ratio of water/methanol is 1.01-1.5; under the microwave radiation, the catalyst bed layer is quickly heated to the working temperature of 180-320 ℃, and the methanol/water mixed raw material is quickly reformed into the main H-containing material under the action of the catalyst 2 And CO 2 The catalyst is prepared from CuO/ZnO composite oxide active component and microwave absorption component, wherein the microwave component is silicon carbide and manganese oxide (MnO) x ) One or more of manganese-cerium composite oxides; the mixed gas is cooled by a cooler 5, a small amount of methanol and water which are not completely converted are condensed, and the obtained mixed condensate of the methanol and the water is collected and stored and recycled into a liquid storage tank A1 to be reused as a raw material; at the same time mainly contain H 2 And CO 2 The mixture gas is primarily dried, then the mixture gas is deeply dried by a deep drying unit 6, and the mixture gas after the deep drying is further subjected to CO 2 The removal unit 7 removes CO therein 2 Thereby obtaining high-purity H 2 And (5) a product.
Example 2
The invention also provides a microwave reforming reaction system, which comprises a liquid storage tank A1, a delivery pump A2, a liquid storage tank B8, a delivery pump B9, a mixer 10, a microwave reactor 4, a cooler 5, a deep drying unit 6 and CO, as shown in figure 2 2 The removal unit 7 is characterized in that a methanol/water mixed solution is stored in a liquid storage tank A1, peroxide is stored in a liquid storage tank B8, the liquid storage tank A1 is connected with a mixer 10 through a delivery pump A2, and the liquid storage tank B8 is communicatedThe mixer 10 is also connected through the delivery pump B9, the other end of the mixer 10 is connected with a feed inlet of the microwave reactor 4, a catalyst bed is filled in the microwave reactor 4, an air outlet of the microwave reactor 4 is connected with the cooler 5, a liquid outlet of the cooler 5 is connected with the liquid storage tank A1, an air outlet of the cooler 5 is connected with an air inlet end of the deep drying unit 6, and an air outlet end of the deep drying unit 6 is connected with CO 2 A removal unit 7.
The reaction process was the same as in example 1, except that the raw material of the methanol/water mixed solution in the reservoir A1 was pumped into the mixer 10 by the transfer pump A2, the raw material of the peroxide in the reservoir B8 was pumped into the mixer 10 by the transfer pump B9, and the mixed solution of methanol/water and peroxide was fed into the tubular microwave reactor 4 preloaded with the catalyst after being mixed in the mixer 10.
Example 3
The invention provides a microwave reforming reaction system, which is shown in figure 3 and comprises a liquid storage tank A1, a delivery pump A2, a pipeline heating vaporizer 3, a microwave reactor 4, a cooler 5, a deep drying unit 6 and CO 2 The removal unit 7 stores mixed solution raw materials in the liquid storage tank A1, the liquid storage tank A1 is connected with one end of the pipeline heating vaporizer 3 through the conveying pump A2, the other end of the pipeline heating vaporizer 3 is connected with a feed inlet of the microwave reactor 4, a catalyst bed is filled in the microwave reactor 4, an air outlet of the microwave reactor 4 is connected with the cooler 5, a liquid outlet of the cooler 5 is connected with the liquid storage tank A1, an air outlet of the cooler 5 is connected with an air inlet end of the deep drying unit 6, and an air outlet end of the deep drying unit 6 is connected with CO 2 A removal unit 7.
The reaction process is the same as that of example 1, except that the methanol/water mixed solution or the raw material of the methanol/water/peroxide mixed solution in the liquid storage tank A1 is vaporized by the pipeline heating vaporizer 3 at a certain flow rate by the delivery pump A2 and then is fed into the tubular microwave reactor 4 preloaded with the catalyst, and the operating temperature of the pipeline heating vaporizer 3 is 100-200 ℃.
Example 4
The invention provides a microwave reforming reaction system, as shown in figure 4, comprising a liquid storage tank A1, a delivery pump A2, a liquid storage tank B8, a delivery pump B9, a pipeline heating vaporizer 3 and a micro-scaleWave reactor 4, cooler 5, deep drying unit 6 and CO 2 The removal unit 7, store methanol/water mixed solution in the liquid storage pot A1, store peroxide in the liquid storage pot B8, the liquid storage pot A1 is connected with the pipeline heating vaporizer 3 through the delivery pump A2, the liquid storage pot B8 is also connected with the pipeline heating vaporizer 3 through the delivery pump B9, the other end of the pipeline heating vaporizer 3 is connected with the feed inlet of the microwave reactor 4, the catalyst bed is filled in the microwave reactor 4, the cooler 5 is connected to the gas outlet of the microwave reactor 4, the liquid outlet of the cooler 5 is connected with the liquid storage pot A1, the gas inlet end of the deep drying unit 6 is connected to the gas outlet of the cooler 5, the CO is connected to the gas outlet end of the deep drying unit 6 2 A removal unit 7.
The reaction process was the same as in example 1, except that the raw material of the methanol/water mixed solution in the liquid tank A1 was pumped into the line heating vaporizer 3 by the transfer pump A2, the raw material of the peroxide in the liquid tank B8 was pumped into the line heating vaporizer 3 by the transfer pump B9, and the methanol/water mixed solution and the peroxide were heated and vaporized in the line heating vaporizer 3 and mixed, and then fed into the tubular microwave reactor 4 preloaded with the catalyst.
Example 5
And (3) preparing a catalyst:
(1) Taking 19.63g of copper nitrate trihydrate and 5.66g of zinc acetate dihydrate (the molar ratio of copper to zinc is 3.15:1), adding 20mL of deionized water and 6g of citric acid monohydrate, mixing and grinding to form a catalyst precursor mixture;
(2) Placing the intermediate product obtained in the step (1) into a baking oven at 150 ℃, keeping the temperature for 1 hour, taking out and stirring for 10 minutes, and placing into the baking oven to dry for 30 minutes until a pasty mixture is formed;
(3) And (3) taking out the product obtained in the step (2), putting the product into a muffle furnace, heating to 550 ℃ at a speed of 10 ℃/min in an air atmosphere, and calcining at 550 ℃ for 1 hour to obtain the catalyst No. 1 (the mass ratio of copper oxide to zinc oxide in the catalyst is 72:28).
(4) 3g of catalyst No. 1 and 2g of manganese dioxide are fully ground for 15min and mixed to form catalyst No. 2.
Microwave driven methanol reforming process:
(1) Loading 5g of catalyst No. 2 into a reaction quartz tube with the length of 60cm and the inner diameter of 12mm, loading the catalyst into the quartz tube with the catalyst and the catalyst into the center of a tubular microwave reactor, wherein the catalyst loading height is 5 cm;
(2) Purging with high purity argon at a concentration of 99.999% at 400mL/min for 10min before the start of the test;
(3) The reaction uses a methanol/water mixed solution (the water/alcohol mole ratio is 1.2:1), the mixed solution is input into a quartz tube through a medium-pressure constant-flow pump with the accuracy of +/-0.5 percent at the flow rate of 0.1mL/min, and a microwave reactor is started at the same time, the power of the reactor is 800W, and the corresponding power density in a microwave cavity is 80kW/m 3 And reacting at different temperatures of 200-250 ℃ to obtain the product.
Under the above conditions, no CO was detected in the range of 200 to 220 ℃. In the temperature range of 200-250 ℃, the content of CO in the product gas increases with the temperature. The maximum CO content reached 0.39mol.% at 250 ℃, the methanol conversion reached 67% at 250 ℃, and the results of example 5 are shown in table 1 and fig. 5.
TABLE 1 microwave methanol reformate compositions and gas velocities at various temperatures in example 5
Example 6
Microwave driven methanol reforming process:
(1) Loading 5g of catalyst No. 2 into a reaction quartz tube with the length of 60cm and the inner diameter of 12mm, loading the catalyst into the quartz tube with the catalyst and the catalyst into the center of a tubular microwave reactor, wherein the catalyst loading height is 5 cm;
(2) Purging with high purity argon at a concentration of 99.999% at 400mL/min for 10min before the start of the test;
(3) The reaction uses a methanol/water/hydrogen peroxide solution with hydrogen peroxide content of 2 wt% (the molar ratio of water to alcohol is 1.2:1), and the methanol/water/hydrogen peroxide solution is pumped into a quartz reaction tube at a flow rate of 0.1mL/min by a medium-pressure constant-flow pump with the precision of +/-0.5%, and a microwave reactor is started at the same time, wherein the power of the reactor is 400W, and the corresponding power density in a microwave cavity is 40kW/m 3 The reaction temperature is controlled within the range of 200-250 ℃ to obtainReformate at different temperatures.
To further compare the microwave process with the conventional thermocatalytic process, the conventional heating-driven methanol reforming process was experimentally examined using the same catalyst, feed conditions, and reaction temperature as in the microwave-driven methanol reforming in this example. The conventional heat driven methanol reforming experiment procedure is as follows:
traditional heating-driven methanol reforming experimental procedure:
(1) Loading 5g of catalyst into a reaction quartz tube with the length of 60cm and the inner diameter of 12mm, loading the catalyst into the quartz tube with the catalyst and the height of 5cm, and loading the quartz tube with the catalyst into the center of a traditional fixed bed reactor;
(2) Purging with high purity argon at a concentration of 99.999% at 400mL/min for 10min before the start of the test;
(3) The reaction was carried out using an aqueous methanol solution (molar ratio of water to alcohol: 1.2:1) having a hydrogen peroxide content of 2wt.% into a quartz tube at a flow rate of 0.1mL/min by means of a medium-pressure constant-flow pump having an accuracy of.+ -. 0.5%, and at the same time heating of the fixed bed was started. And maintaining the temperature to be between 200 and 250 ℃ for reaction to obtain the product.
The results of microwave-driven and conventional heat-driven methanol reforming are shown in tables 2 and 3. As a result of the analysis experiment, compared with example 5, the microwave power required by the reaction of microwave-driven methanol reforming in example 6 is reduced to 400W, but the methanol conversion rate is greatly improved compared with that when hydrogen peroxide is not added, which means that the hydrogen peroxide is improved in the methanol conversion rate and the performance of hydrogen production by catalytic reforming of methanol is enhanced. The results in table 2 show that the microwave driven methanol reforming process has very significant advantages over conventional heating processes in the temperature range of 200-230 c, with higher methanol conversion. The method has the advantages of reflecting the great potential of microwave-driven methanol high-efficiency reforming hydrogen production at lower temperature.
Table 2 microwave-driven methanol reformate compositions and gas velocities at different temperatures in example 6
TABLE 3 conventional heating driven methanol reformate compositions and gas velocities at various temperatures for example 6
Example 7
Microwave driven methanol reforming process: experimental procedure As in example 6, except that the reactor power of the microwave reactor was 220W and the corresponding power density in the microwave cavity was 22kW/m 3 . The reaction was carried out at 250℃for a long period of time to give the product.
Under the above conditions, the required microwave power was further reduced to 220W, and the gas product analysis results are shown in table 4. As shown in the results of Table 4, the CO content in the product can be well maintained below 0.47 mol%, and the methanol conversion rate is stably maintained within the range of 72.5-79%, which proves that the microwave-driven methanol reforming hydrogen production process has good stability.
Table 4 composition and gas velocity of reaction product of microwave-driven methanol reforming hydrogen production at 250 DEG C
Example 8
And (3) preparing a catalyst:
(1) Taking 4.32g of copper nitrate trihydrate and 1.68g of zinc acetate dihydrate (the molar ratio of copper to zinc is 2.33:1), adding 20mL of deionized water and 3g of citric acid monohydrate, and stirring to form a transparent solution;
(2) Adding 4g of manganese dioxide into the solution obtained in the step (1), stirring at the normal temperature of 25 ℃ for 3 hours, heating to 140 ℃ and evaporating to dryness;
(3) And (3) taking out the product obtained in the step (2), putting the product into a muffle furnace, heating to 550 ℃ at a speed of 10 ℃/min in an air atmosphere, and calcining for 1 hour to obtain the catalyst 3# (the mass ratio of copper oxide to zinc oxide to manganese dioxide in the catalyst is 43:17:40).
Microwave driven methanol reforming process:
(1) Loading 5g of catalyst 3# into a reaction quartz tube with the length of 60cm and the inner diameter of 12mm, loading the catalyst into the quartz tube with the catalyst at the height of 5cm, and loading the quartz tube with the catalyst into the center of a tubular microwave reactor;
(2) Purging with high purity argon at a concentration of 99.999% at 400mL/min for 10min before the start of the test;
(3) The reaction uses methanol aqueous solution (the water/alcohol mole ratio is 1.05:1) to be input into a quartz tube through a medium-pressure constant-flow pump with the accuracy of +/-0.5 percent at the flow rate of 0.1mL/min, and simultaneously a microwave reactor is started, and the power of the reactor is 220W. The reaction was carried out at 235℃for a long period of time to obtain reformate, and the results are shown in Table 5.
From the results of Table 5, it is apparent that an effective microwave-driven catalyst for reforming methanol to produce hydrogen can also be obtained by a catalyst preparation method in which copper-zinc active components are supported on a carrier such as manganese dioxide.
Table 5 product composition and gas velocity for long-time microwave driven methanol reforming hydrogen production at 235 DEG C
The catalyst for preparing hydrogen by reforming methanol, which is adopted in the hydrogen preparation method, takes CuO/ZnO as a main active component. Unlike traditional reforming catalyst suitable for thermal catalysis, the catalyst for microwave catalysis process must also consider the microwave absorption, and the microwave absorption by the catalytic material is converted into heat and electric potential energy, and the interaction between the active component and the carrier interface can have great influence on the microwave-driven methanol reforming hydrogen production reaction performance. Thus, the microwave catalyst used in the present invention is made of a CuO/ZnO composite oxide active component and a microwave absorbing component, and the microwave component may be one or more of silicon carbide and manganese cerium composite oxide in addition to manganese dioxide in the above embodiments. Wherein, the silicon carbide and the manganese oxide can be selected from commercial products with 60 to 250 meshes, and the preferable mesh number is 100 to 150 meshes. In addition, the manganese oxide can be self-made, and the preparation method is that one or more of manganese nitrate, manganese acetate and manganese citrate are used as precursors, and the manganese oxide is obtained by calcining in air and grinding to 100-150 meshes, wherein the calcining temperature is 450-750 ℃, and the calcining temperature is 500-600 ℃ preferably.
The manganese-cerium composite oxide can also be self-made, and the preparation method comprises the following steps: manganese dioxide or manganese nitrate is fully mixed with citric acid monohydrate of which the mass is 3 to 8 times that of the manganese dioxide or manganese nitrate, water of which the mass is 4 to 10 times that of the mixture is added, and the mixture is heated to 60 to 90 ℃ to form yellow-brown transparent solution. Then adding cerium nitrate or cerium acetate as a precursor of cerium oxide into the solution to form a new mixed solution, evaporating water in the new mixed solution within the range of 100-200 ℃, and calcining the dried mixture in air at 500-650 ℃ to obtain the required manganese-cerium composite oxide, wherein the calcining temperature is preferably 530-570 ℃; in the preparation process, the molar ratio of manganese to cerium is 10-40, and the preferable molar ratio of manganese to cerium is 15-23.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (9)
1. The microwave-driven methanol reforming rapid hydrogen production method is characterized by comprising the following steps of:
directly pumping the raw material of the methanol/water mixed solution in the liquid storage tank A into a tubular microwave reactor preloaded with a catalyst, wherein the molar ratio of water/methanol is 1.01-1.5; peroxide is also mixed in the liquid storage tank A to prepare a methanol/water/peroxide mixed raw material; or storing the peroxide in a liquid storage tank B, respectively pumping and mixing the methanol/water mixed raw material and the peroxide, and then entering a tubular microwave reactor, wherein the content of the total peroxide in the methanol/water/peroxide mixed raw material is controlled to be 0.1-3 wt%; the peroxide is hydrogen peroxide;
under the microwave radiation, the catalyst bed is quickly heated to the working temperature of 200-250 ℃, and the methanol/water mixed raw material is quickly reformed into a main H-containing material under the action of the catalyst 2 And CO 2 The catalyst is prepared from a CuO/ZnO composite oxide active component and a microwave absorption component, wherein the microwave absorption component is one or more of silicon carbide, manganese oxide and manganese cerium composite oxide;
the mixed gas is cooled and then condensed with a small amount of methanol and water which are not completely converted, and the obtained mixed condensate of methanol and water is collected, stored and circulated into a liquid storage tank A to be reused as a raw material;
at the same time mainly contain H 2 And CO 2 The mixture gas is primarily dried, then the mixture gas is deeply dried by a deep drying unit, and the mixture gas after the deep drying is further subjected to CO 2 Removing to obtain H 2 And (5) a product.
2. The method for microwave-driven rapid hydrogen production by methanol reforming according to claim 1, wherein the content of the total hydrogen peroxide in the methanol/water/peroxide mixed raw material is controlled to be 0.5-2 wt%.
3. The method for quickly producing hydrogen by reforming methanol under microwave drive according to claim 1, wherein the catalyst is obtained by mechanically mixing a CuO/ZnO composite oxide active component and a microwave absorbing component, and the mass ratio of the CuO/ZnO composite oxide active component to the microwave absorbing component is 0.8-2.5.
4. The method for quickly producing hydrogen by reforming methanol under microwave drive according to claim 1, wherein the catalyst is obtained by loading CuO/ZnO composite oxide active components on the surface of a microwave absorbing component, and the mass ratio of the CuO/ZnO composite oxide active components to the microwave absorbing component is 0.6-2.
5. The method for rapidly producing hydrogen by reforming methanol under microwave drive according to claim 1, 3 or 4, wherein the molar ratio of Cu to Zn in the CuO/ZnO composite oxide active ingredient is 1.5 to 4.
6. The method for quickly producing hydrogen by reforming methanol under the drive of microwaves according to claim 1, wherein the preparation process of the active component of the CuO/ZnO composite oxide is as follows: mixing a copper precursor and a zinc precursor corresponding to the Cu/Zn molar ratio, adding citric acid monohydrate with the mass of 0.2-1 times of that of the precursor mixture, adding distilled water with the total mass of 0.5-5 times of that of the mixture, uniformly mixing at 100-160 ℃, evaporating to dry the water, and finally calcining in the air at 450-600 ℃ for 1-3 hours.
7. The method for microwave-driven methanol reforming and rapid hydrogen production as in claim 4, wherein the loading method is as follows: mixing a copper precursor and a zinc precursor corresponding to the Cu/Zn molar ratio, adding citric acid monohydrate with the mass of 0.5-1.5 times of that of the precursor mixture, adding distilled water with the total mass of 4-10 times of that of the mixture, dissolving to form a transparent solution, adding a microwave absorption component into the transparent solution, evaporating water under the stirring condition to form a viscous mixed slurry, and finally calcining in the air at 500-650 ℃ for 1-3 hours.
8. The method for microwave-driven methanol reforming and rapid hydrogen production according to claim 6 or 7, wherein the copper precursor is one or more of copper nitrate and hydrate thereof, copper acetate and hydrate thereof; the zinc precursor is one or more of zinc nitrate and hydrate thereof, zinc acetate and hydrate thereof, zinc chloride and hydrate thereof, and zinc hydroxide.
9. The method for quickly producing hydrogen by reforming methanol under microwave drive according to claim 1 or 2, wherein the radiation power density of microwaves is controlled to be 20-400 kw/m during the reaction process 3 。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200266A (en) * | 2004-01-15 | 2005-07-28 | Casio Comput Co Ltd | Reforming method, reformer, power generator and fuel vessel |
| CN104157889A (en) * | 2014-08-06 | 2014-11-19 | 上海工程技术大学 | Methanol steam reforming hydrogen production reactor for fuel cell car |
| CN109078590A (en) * | 2017-06-13 | 2018-12-25 | 中国石油化工股份有限公司 | Micro passage reaction |
| CN112547074A (en) * | 2020-12-14 | 2021-03-26 | 川化集团有限责任公司 | Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof |
| CN113731429A (en) * | 2021-09-26 | 2021-12-03 | 厦门大学 | Copper-based catalyst for hydrogen production by methanol steam reforming, and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200266A (en) * | 2004-01-15 | 2005-07-28 | Casio Comput Co Ltd | Reforming method, reformer, power generator and fuel vessel |
| CN104157889A (en) * | 2014-08-06 | 2014-11-19 | 上海工程技术大学 | Methanol steam reforming hydrogen production reactor for fuel cell car |
| CN109078590A (en) * | 2017-06-13 | 2018-12-25 | 中国石油化工股份有限公司 | Micro passage reaction |
| CN112547074A (en) * | 2020-12-14 | 2021-03-26 | 川化集团有限责任公司 | Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof |
| CN113731429A (en) * | 2021-09-26 | 2021-12-03 | 厦门大学 | Copper-based catalyst for hydrogen production by methanol steam reforming, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Rational design of mesoporous MnO2 microwave absorber with tunable microwave frequency response;Gaihua He et al.;《Applied Surface Science》;摘要 * |
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