CN117181230A - Catalytic adsorbent, preparation method thereof and method for preparing hydrogen by reforming methanol steam - Google Patents
Catalytic adsorbent, preparation method thereof and method for preparing hydrogen by reforming methanol steam Download PDFInfo
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Abstract
The invention relates to the field of catalysts, and discloses a catalytic adsorbent, a preparation method thereof and a method for preparing hydrogen by reforming methanol steam, wherein the catalytic adsorbent comprises CuO as a component x ‑MgO‑Ga 2 O 3 Is a composite material of (a); wherein x is more than 0 and less than or equal to 1; based on the total amount of the catalytic adsorbent, cuO is calculated as CuO x The content of (2) is 10-20wt%, the content of MgO is 70-74wt%, and Ga 2 O 3 The content of (2) is 10-20wt%; the surface roughness of the catalyst adsorbent is 1-4/mu m 2 . The catalytic adsorbent has high catalytic activity, can realize high-efficiency conversion of methanol at a lower temperature, effectively inhibit reverse water-gas shift and reduce the content of CO in reformate. The self-heating operation of the whole reaction can be realized through the heat absorption and release balance of the reforming reaction and the regeneration reaction,the energy loss in the reaction process is reduced, and the engineering application feasibility of the adsorption-enhanced methanol steam reforming technology for preparing high-purity hydrogen is improved.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalytic adsorbent, a preparation method thereof and a method for preparing hydrogen by reforming methanol steam.
Background
With the increasing global energy crisis and environmental pollution problems, the development of clean and environment-friendly new energy is imperative. The hydrogen energy is used as an energy carrier with high energy density, clean and pollution-free products, flexible in utilization form, widely applied to the fields of aerospace, fine chemical industry, food processing, metal smelting and the like, and will occupy an important position in a future energy structure. In addition, the rapid development of fuel cells in recent years has led to the introduction of hydrogen energy utilization into a new era, and the application of hydrogen energy fuel cell technology in the field of distributed, mobile system (e.g., automobile) energy supply has been attracting attention. However, the problems of high-efficiency and low-cost preparation and storage and transportation of hydrogen always restrict the commercialization popularization of hydrogen energy.
Methanol is an ideal hydrogen carrier, and has a high H/C molar ratio, a low reforming temperature (no C-C bond, less than 300 ℃ C.), and a high hydrogen storage (148.5 g.H) 2 /L·CH 3 OH, theoretical methanol steam reforming), no sulfur nitrogen and other elements, and is convenient to transport as liquid fuel. The hydrogen energy can be safely, efficiently and cleanly prepared and stored in real time by reforming the methanol in situ into the hydrogen energy fuel cell for supplying hydrogen.
Existing methanol reforming routes mainly include Steam Reforming (SR)M，H 2 /CO 2 About 3), partial oxidation of methanol (POM, H 2 /CO 2 Approximately 2), methanol oxidation reforming (OSRM, 2<H 2 /CO 2 <3). Among them, SRM theory can produce hydrogen with the highest concentration and yield, and is a more common reforming hydrogen production mode. However, the SRM has problems in that by-product CO generated during the reaction thereof 2 Not only reduces the concentration of hydrogen, but also generates CO to poison the Pt electrode of the fuel cell through reverse water vapor change reaction, thereby reducing the working efficiency and the service life of the fuel cell. In addition, the SRM reforming temperature is high under the limit of catalyst property and reaction thermodynamic equilibrium, and adverse side reactions such as methanol pyrolysis, reverse water-gas shift and the like are aggravated while the hydrogen production energy consumption is increased. Higher reaction temperatures can also lead to deactivation of the active components, reducing the reaction stability of the catalyst.
Adsorption enhanced methanol steam reforming hydrogen production technology (SE-SRM) can be achieved by coupling SRM and CO 2 The adsorption reaction promotes the forward progress of the reforming hydrogen production reaction and the water gas shift reaction, reduces the reaction temperature, improves the methanol conversion rate and improves the purity of the hydrogen. By CO 2 In-situ removal of the hydrogen, the SE-SRM only uses one reactor to complete the preparation and purification process of the hydrogen, and the hydrogen produced under ideal conditions can directly meet the continuous and stable operation requirement of the fuel cell without additional CO and CO 2 The removing device has the obvious advantages of simple system, high volume efficiency and energy efficiency, wide application range and the like. However, the existing SE-SRM technology still has some technical difficulties to be solved, such as easy deactivation of the catalyst and easy CO during the high-temperature regeneration process 2 Low adsorption capacity, low CO content and low methanol reforming temperature.
Disclosure of Invention
The invention aims to overcome the defects that a methanol steam reforming catalyst is easy to deactivate and CO in the high-temperature regeneration process in the prior art 2 The problems of low adsorption capacity and further reduction of CO content and methanol reforming temperature are solved, and a catalytic adsorbent, a preparation method thereof and a method for preparing hydrogen by reforming methanol steam are provided, wherein the catalytic adsorbent has higher catalytic activity and can realize high methanol content at lower temperatureEfficient conversion and CO realization 2 Is in situ captured.
In order to achieve the above object, a first aspect of the present invention provides a catalytic adsorbent comprising CuO as a component x -MgO-Ga 2 O 3 A composite material; wherein x is more than 0 and less than or equal to 1;
based on the total amount of the catalytic adsorbent, cuO is calculated as CuO x The content of (2) is 10-20wt%, the content of MgO is 70-74wt%, and Ga 2 O 3 The content of (2) is 10-20wt%;
wherein the surface roughness of the catalytic adsorbent is 1-4/mu m 2 。
The second aspect of the present invention provides a method for producing a catalytic adsorbent, comprising the steps of:
(1) Mixing a Cu source, a Mg source and a Ga source with a gel auxiliary agent in the presence of a solvent to obtain a mixed solution;
(2) Under the stirring condition, carrying out gelation reaction on the mixed solution, and then carrying out heat treatment on a product obtained by the reaction;
wherein the Cu source, the Mg source and the Ga source are used in such an amount that CuO is calculated as CuO based on the total amount of the catalyst adsorbent x The content of (2) is 10-20wt%, the content of MgO is 70-74wt%, and Ga 2 O 3 The content of (C) is 10-20wt%.
The third aspect of the present invention provides a catalyst adsorbent prepared by the above preparation method.
In a fourth aspect, the present invention provides a method for producing hydrogen by steam reforming methanol, the method comprising: under the condition of reforming methanol steam, contacting methanol water solution steam with a catalytic adsorbent to obtain hydrogen and CO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein CO 2 The catalytic adsorbent is used for adsorption to realize in-situ removal;
the catalytic adsorbent is the catalytic adsorbent provided in the first aspect and the third aspect.
Preferably, the catalytic adsorbent is not subjected to reductive activation prior to use.
The catalytic adsorbent provided by the invention has higher catalytic activity and can realize lower catalytic activityThe high-efficiency conversion of methanol at the temperature can effectively inhibit the reverse water gas shift and reduce the content of CO in the reformate. By means of CuO in the catalytic adsorbent component x -MgO-Ga 2 O 3 Certain electron transfer and interaction exist between the two, and through the synergistic effect, migration, agglomeration and inactivation of Cu species in the reaction process can be effectively inhibited, and CuO is adopted x The lattice oxygen in the catalyst induces the steam autothermal reforming of methanol oxidation, effectively improves the conversion rate of methanol, can improve the property and distribution condition of alkaline sites on the surface of the catalyst through the regulation and control of the surface roughness of the catalytic adsorbent, and promotes CO 2 Adsorption capacity and improved adsorption and desorption characteristics, thereby reducing regeneration temperature and improving the cycle stability of the catalytic adsorbent.
The method for preparing hydrogen by reforming methanol steam provided by the invention adopts the catalytic adsorbent provided by the invention, the self-heating operation of the whole reaction can be realized through the self-heating balance of the oxidation-reduction reaction absorption and heat release in the methanol oxidation steam self-heating reforming and regeneration stage, the energy loss in the reaction process is reduced, and the engineering application feasibility of the adsorption-enhanced methanol steam reforming high-purity hydrogen technology is improved.
Drawings
FIG. 1 is a schematic illustration of the reaction process of the present invention for steam reforming of methanol to produce hydrogen and in situ regeneration;
FIG. 2 is a system flow diagram for the Aspen Plus system flow simulation software calculation;
FIG. 3 is a heat load distribution of the methanol to hydrogen reactor calculated by Aspen Plus system flow simulation software;
FIG. 4 is a thermal load distribution of the regeneration reactor calculated by Aspen Plus system flow simulation software.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a catalytic adsorbent comprising CuO as a component x -MgO-Ga 2 O 3 Is a composite material of (a); wherein x is more than 0 and less than or equal to 1;
based on the total amount of the catalytic adsorbent, cuO is calculated as CuO x The content of (2) is 10-20wt%, the content of MgO is 70-74wt%, and Ga 2 O 3 The content of (2) is 10-20wt%;
wherein the surface roughness of the catalytic adsorbent is 1-4/mu m 2 。
As will be appreciated by those skilled in the art, cuO x And x in (2) represents the amount of oxygen in the lattice. The catalyst adsorbent can be a freshly prepared catalyst adsorbent or a regenerated catalyst adsorbent obtained after reaction regeneration. The catalytic adsorbent is in a reducing atmosphere in the methanol reforming hydrogen production process, so that lattice oxygen can migrate to the surface from the bulk phase and participate in the oxidation steam reforming hydrogen production reaction of the methanol, thereby forming oxygen vacancy defects and further promoting the adsorption activation of the methanol. Wherein, the range of x is: 0<x≤1。
According to the invention, cuO in the catalytic adsorbent component x -MgO-Ga 2 O 3 Certain electron transfer and interaction exist between the two, and through the synergistic effect, migration, agglomeration and inactivation of Cu species in the reaction process can be effectively inhibited, and CuO is adopted x The lattice oxygen in the catalyst induces the steam autothermal reforming of methanol oxidation, so that the conversion rate of methanol can be effectively improved, and meanwhile, a rich spike-shaped protrusion structure is formed on the surface through the regulation and control of the surface roughness of the catalyst, so that the high dispersion of reactive sites is promoted; can improve the property and distribution of the alkaline sites on the surface of the catalyst and promote CO 2 Adsorption capacity and improved adsorption and desorption characteristics, thereby reducing regeneration temperature and improving the cycle stability of the catalytic adsorbent.
In the present invention, the autothermal reaction means that the reforming reaction is spontaneously performed under the participation of lattice oxygen without external heat.
In the invention, aspen Plus system flow simulation software is adopted to calculate the energy distribution of the methanol reforming hydrogen production stage and the catalytic adsorbent regeneration stage, and the reaction process is proved to be self-heating reaction when the heat load is more than 0.
In the invention, the surface roughness of the catalytic adsorbent refers to the number of protrusions corresponding to a unit area under an atomic force microscope. The surface of the catalytic adsorbent was subjected to atomic force microscopy at 25. Mu.m 2 And counting the number of bulges under the area, and obtaining the surface roughness under the unit area through calculation.
In the present invention, preferably, the surface roughness of the catalyst adsorbent is 1.5 to 3 pieces/μm 2 . In the above preferred case, it is advantageous to further improve the adsorption/desorption performance of the catalyst adsorbent.
In the present invention, preferably, cuO is calculated as CuO based on the total amount of the catalytic adsorbent x The content of (2) is 11-17wt%, the content of MgO is 70-73wt%, and Ga 2 O 3 The content of (C) is 12-17wt%. In the above preferred case, it helps to build up strong interactions between the components, improving the catalytic activity and CO of the catalytic adsorbent 2 Adsorption and desorption stability.
In the present invention, the contents of the components were tested by inductively coupled plasma emission spectroscopy.
In the present invention, preferably, cuO in the catalytic adsorbent is calculated as an element x 、MgO、Ga 2 O 3 The molar ratio of (1) is (0.07-0.18): 1: (0.07-0.09), preferably (0.10-0.16): 1: (0.08-0.09). In the above preferred case, further exertion of CuO is facilitated x -MgO-Ga 2 O 3 Synergistic effect between the two to increase surface defects, thereby preferentially promoting CO 2 Adsorption and activation of methanol molecules on the surface of the catalytic adsorbent to promote CO 2 Low-temperature desorption of the material is inhibited.
The second aspect of the present invention provides a method for producing a catalytic adsorbent, comprising the steps of:
(1) Mixing a Cu source, a Mg source, a Ga source, a gel auxiliary agent and water to obtain a mixed solution;
(2) Under the stirring condition, carrying out gelation reaction on the mixed solution, and then carrying out heat treatment on a product obtained by the reaction;
wherein the Cu source, the Mg source and the Ga source are used in such an amount that CuO is calculated as CuO based on the total amount of the catalyst adsorbent x The content of (2) is 10-20wt%, the content of MgO is 70-74wt%, and Ga 2 O 3 The content of (C) is 10-20wt%.
In the invention, the catalyst adsorbent obtained by the preparation method is prepared by CuO x -MgO-Ga 2 O 3 The surface of the polymer has rich spike-shaped protrusion structures, has proper surface roughness and promotes the high dispersion of reactive sites. The obtained catalyst adsorbent has higher catalytic activity and excellent CO in the methanol steam reforming reaction 2 Adsorption and desorption properties.
According to the present invention, preferably, the Cu source, the Mg source and the Ga source are used in such amounts that CuO is calculated as CuO based on the total amount of the catalytic adsorbent x The content of (2) is 11-17wt%, the content of MgO is 70-73wt%, and Ga 2 O 3 The content of (C) is 12-17wt%. The adoption of the preferred embodiment helps to construct strong interaction between the components, and further improves the catalytic activity and CO of the catalytic adsorbent 2 Adsorption and desorption stability.
According to the present invention, it is preferable that the molar ratio of the Cu source, mg source and Ga source is (0.07 to 0.18) in terms of elements: 1: (0.07-0.09), preferably (0.10-0.16): 1: (0.08-0.09). In the above preferred case, further exertion of CuO is facilitated x -MgO-Ga 2 O 3 Synergistic effect between the two to increase surface defects, thereby preferentially promoting CO 2 Adsorption and activation of methanol molecules on the surface of the catalytic adsorbent to promote CO 2 Low-temperature desorption of the material is inhibited.
According to the present invention, it is preferable that the total concentration of the Cu source, the Mg source and the Ga source in the mixed liquid is 0.5 to 2mol/L, preferably 0.8 to 1.2mol/L, in terms of metal element. The adoption of the preferred embodiment is beneficial to improving the surface roughness of the catalytic adsorbent, forming a defect structure and further promoting the low-temperature activation of methanol.
According to the present invention, preferably, the ratio of the molar amount of the gel aid to the total molar amount of the Cu source, mg source and Ga source in terms of metal elements is 1 to 2:1, preferably 1.1-1.5:1.
in the present invention, the selection range for the specific kinds of Cu source, mg source and Ga source is wide, and may be each independently selected from soluble salts of metals selected from inorganic salts and/or organic matters. Preferably, the Cu source, mg source and Ga source are each independently selected from at least one of nitrate, chloride, and acetate of a metal, further preferably nitrate. With the preferred embodiments described above, a better foaming precursor is advantageously obtained.
In the present invention, the selection of the gel aid is well known to those skilled in the art, preferably the gel aid is selected from at least one of citric acid, ethylene glycol, glucose and starch, further preferably citric acid and/or polyethylene glycol.
According to a preferred embodiment of the invention, the Cu source, the Mg source and the Ga source are respectively selected from metal nitrate, and when the gel auxiliary agent is citric acid, the synergistic effect of the metal salt and the gel auxiliary agent is further exerted, and the precursor material of the foaming material with better performance is formed.
In the present invention, the specific parameters of stirring in step (2) may be adjusted according to experimental practice as long as the gelation reaction can be achieved. Preferably, the stirring speed is 100-1500rpm, more preferably 300-800rpm.
In the present invention, the specific operation of the gelation reaction is well known to those skilled in the art, and for example, the gelation reaction may be performed using a water bath.
According to the present invention, preferably, the temperature of the gelation reaction is 30 to 90 ℃, further preferably 60 to 80 ℃; the use of the above-described preferred gelation conditions facilitates the formation of a more uniform, stable gel precursor.
According to the present invention, preferably, the heat treatment includes: and drying and roasting the product obtained by the reaction. The book is provided withThe inventors of the present invention have found in the study that the surface roughness of the prepared catalytic adsorbent is affected by the combination of the composition of the catalytic adsorbent and the conditions of the heat treatment. To obtain proper surface roughness, the catalytic activity and CO of the catalytic adsorbent are improved 2 The adsorption and desorption properties, preferably, the drying conditions include: the drying temperature is 130-200deg.C, preferably 150-170deg.C, and the drying time is 5-16 hr, preferably 10-12 hr. Too high a drying temperature may result in volatilization of the gel auxiliary agent, while the surface carbon is serious, and when the drying temperature is too low, gel foaming is not facilitated.
In the invention, the preparation method further comprises grinding the dried product and then roasting.
According to the present invention, preferably, the firing includes: heating to 300-500 ℃ at a heating rate of 1-3 ℃/min, and then roasting at the temperature for 1-10h.
The third aspect of the present invention provides a catalyst adsorbent prepared by the above preparation method.
In a fourth aspect, the present invention provides a method for producing hydrogen by steam reforming methanol, the method comprising: under the condition of reforming methanol steam, contacting the methanol steam with a catalytic adsorbent to obtain hydrogen and CO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein CO 2 The catalytic adsorbent is used for adsorption to realize in-situ removal;
the catalytic adsorbent is the catalytic adsorbent provided in the first aspect or the third aspect.
According to the invention, in the process of preparing hydrogen by reforming methanol steam, when the methanol steam contacts with the catalytic adsorbent, cuO in the components in the catalytic adsorbent x Lattice oxygen induced autothermal reforming of methanol oxidation steam with CO as a reaction byproduct 2 The MgO in the catalytic adsorbent is adsorbed and removed; because the catalyst has proper surface roughness, a rich spike-shaped protruding structure is formed on the surface, the high dispersion of reactive sites is promoted, the catalytic activity is high, the conversion rate of methanol in the reaction of preparing hydrogen by reforming methanol steam is high, and the continuous preparation of high-concentration hydrogen and CO can be realized 2 Trapping to effectively inhibit CO generation, so that reformed gas can be directly introduced into hydrogenCan be used for fuel cells without the need for subsequent CO oxidation treatment.
According to the invention, the catalytic adsorbent is preferably not subjected to reductive activation prior to use. The catalyst in the prior art usually needs to be subjected to reduction activation before use to obtain higher catalytic activity, but the inventor of the invention discovers in research that the catalytic adsorbent has proper surface roughness, has multiple reactive sites on the surface and good dispersibility, can obtain higher catalytic activity without reduction, and meanwhile, cuO in the components x The lattice oxygen in the catalyst is favorable for inducing the autothermal reforming of methanol oxidation steam, and can further improve the conversion rate of methanol in the reaction.
In the present invention, the contacting may be performed in a reactor conventional in the art, such as a fixed bed reactor or a fluidized bed reactor, preferably, the contacting is performed in a fixed bed reactor.
In order to ensure higher methanol conversion rate and higher reaction temperature, the method provided by the invention can realize high-efficiency conversion of methanol at lower temperature; at the same time, the lower reforming temperature is also beneficial to realizing the thermal combination between the methanol reforming chamber and the hydrogen energy fuel cell. Preferably, the methanol steam reforming conditions include: the molar ratio of water to methanol is 1.2-4:1, preferably 2-3:1, a step of; the volume space velocity of the methanol is 200-800h -1 Preferably 300-600h -1 The reaction temperature is 180-240 ℃, preferably 190-220 ℃; the reaction pressure is 0.1-0.2MPa, preferably 0.10-0.15MPa.
According to the present invention, preferably, the method further comprises regenerating the catalyst adsorbent after the reaction. Preferably, the regenerating comprises: and (3) in-situ regenerating the catalytic adsorbent under an oxygen-containing atmosphere.
It will be appreciated by those skilled in the art that the timing of regeneration of the catalytic adsorbent may be selected based on the actual reaction schedule, e.g., CO may be adsorbed at the catalytic adsorbent 2 Regenerating the catalytic adsorbent after saturation, judging adsorption saturation by mass change and mass change rate of a thermogravimetric curve, wherein the operation isAs is well known to those skilled in the art.
Conventional catalyst regeneration reactions are typically carried out under inert atmospheres such as nitrogen, but prior art steam reforming of methanol to produce hydrogen and CO 2 The desorption catalyst regeneration reactions are all strong endothermic reactions, and the reaction energy consumption is extremely high. The inventors of the present invention have creatively found that by catalyzing CuO in an adsorbent x The oxidation-lattice oxygen release (reduction) circulation process can realize the self-heating operation of the reforming hydrogen production reaction and the regeneration reaction, and the reaction energy consumption is obviously reduced.
The reaction process of steam reforming methanol to produce hydrogen and in situ regeneration according to the present invention is shown in figure 1. In the reforming reaction, the active component CuO x Catalytic oxidation of methanol to steam reforming to H 2 With CO 2 Alkaline metal oxide MgO of intercalation phase adsorbs reforming byproduct CO 2 Generating Cu-MgCO 3 -Ga 2 O 3 The reaction processes are all exothermic reactions, and heat can be supplied for the reforming reaction; in the regeneration process, mgCO is reacted under the oxygen-containing atmosphere 3 Desorption of CO 2 MgO is generated and Cu is used for CuO at the same time x The oxidation reaction of (2) supplies heat for desorption reaction, and based on the effects, the CO can be realized by regulating and controlling the component content in the catalyst 2 The self-heating operation of desorption and catalyst regeneration reaction improves the energy efficiency.
In the present invention, preferably, the conditions for the regeneration include: the regeneration temperature is 300-400 ℃, preferably 320-360 ℃; the volume space velocity of the oxygen-containing atmosphere is 200-500h -1 Preferably 300-400h -1 The method comprises the steps of carrying out a first treatment on the surface of the Mg-based adsorbent CO in the prior art 2 The desorption temperature is higher (generally 400-420 ℃), which is easy to cause the sintering deactivation of the adsorbent, and the CuO is adopted in the invention x -MgO-Ga 2 O 3 Synergistic effect of the two, CO is adsorbed in reforming reaction 2 Can generate more bidentate carbonates which are easier to desorb, and is favorable for realizing CO at lower temperature 2 And (3) high-efficiency desorption is carried out, and the regeneration of the catalytic adsorbent is completed.
In the present invention, the oxygen-containing atmosphere may be oxygen or oxygen and CO 2 Is a mixed gas of (1); preferably, the oxygen-containing atmosphereIs CO 2 With O 2 Wherein CO is 2 And O 2 The volume ratio of (2) is 8-20:1, further preferably 12-20:1. under the preferred embodiment, the efficient desorption and regeneration of the adsorbent are facilitated, and high-quality CO is obtained 2 And (3) gas.
The present invention will be described in detail by examples.
The starting materials in the examples below were all from commercial sources.
In the following examples, the surface roughness was 25 μm on the surface of the catalyst adsorbent by atomic force microscopy 2 And counting the number of protrusions under the area, and recording the number of protrusions corresponding to the unit area as the surface roughness of the catalytic adsorbent.
The energy distribution of the methanol reforming hydrogen production stage and the catalytic adsorbent regeneration stage is calculated by Aspen Plus system flow simulation software, and the system flow chart is shown in figure 2.
The calculated parameters are as follows:
physical parameters: PENG-ROB
Logistics type: MIXCISLD
Type of reforming reactor: RGibbs
Type of regeneration reactor: RGibbs
Type of heat exchanger: heatX
The following preparation examples are presented to illustrate the preparation of the catalytic adsorbents.
Preparation example 1
(1) The molar ratio was set to 0.07:1: cu (NO) of 0.07 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Ga(NO 3 ) 3 ·xH 2 O and citric acid are dissolved in deionized water, the molar concentration of total metal cations is controlled to be 1mol/L, and the ratio of the molar quantity of the citric acid to the total molar quantity of the metals is 1.2:1.0.
(2) The above mixture was vigorously stirred in a water bath at a reaction temperature of 40℃and at a stirring rate of 600rpm until a gel formed.
The gel obtained by the reaction was then dried in a dry oven at 170 ℃ for 10 hours, and then the obtained precursor was ground into fine powder. Finally, the powder is heated to 450 ℃ in a muffle furnace at a heating rate of 2.5 ℃/min, and calcined for 4 hours at 450 ℃ to obtain the catalytic adsorbent A1, wherein the surface morphology of the catalytic adsorbent material is shown in figure 2, and the composition and the surface roughness data are shown in table 1.
Preparation example 2
(1) The molar ratio was set to 0.08:1: cu (NO) of 0.09 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Ga(NO 3 ) 3 ·xH 2 O and citric acid are dissolved in deionized water, the molar concentration of total metal cations is controlled to be 0.1mol/L, and the ratio of the molar quantity of the citric acid to the total molar quantity of the metals is 1.3:1.
(2) The above mixture was vigorously stirred in a water bath at a reaction temperature of 60℃and a stirring rate of 800rpm until gel was formed.
The gel obtained by the reaction was then dried in a dry oven at 170 ℃ for 5 hours, and then the obtained precursor was ground into fine powder. Finally, the powder was heated to 450 ℃ in a muffle furnace at a heating rate of 2.5 ℃/min and calcined at 450 ℃ for 4 hours to obtain a catalytic adsorbent A2, and the composition and surface roughness data are shown in table 1.
Preparation example 3
(1) The molar ratio was set to 0.12:1: cu (NO) of 0.09 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Ga(NO 3 ) 3 ·xH 2 O and citric acid are dissolved in deionized water, the molar concentration of total metal cations is controlled to be 0.1mol/L, and the ratio of the molar quantity of the citric acid to the total molar quantity of the metals is 1.2:1.
(2) The above mixture was vigorously stirred in a water bath at a reaction temperature of 80℃and at a stirring rate of 1200rpm until gel was formed.
The gel obtained by the reaction was then dried in a dry box at 150 ℃ for 10 hours, and then the obtained precursor was ground into fine powder. Finally, the powder was heated to 450 ℃ in a muffle furnace at a heating rate of 2.5 ℃/min and calcined at 450 ℃ for 4 hours to obtain a catalytic adsorbent A3, the composition and surface roughness data are shown in table 1.
Preparation example 4
The procedure of preparation 1 was followed except that the gel obtained by the reaction was dried in a drying oven at 130℃for 6 hours. The resulting catalyst was A4 and the composition and surface roughness data are shown in table 1.
Preparation example 5
The procedure of preparation 1 was followed except that the gel obtained by the reaction was dried in a drying oven at 160℃for 10 hours. The resulting catalyst was A5 and the composition and surface roughness data are shown in table 1.
Preparation example 6
According to the method in preparation example 1, except that Cu (NO 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Ga(NO 3 ) 3 ·xH 2 The molar ratio of O is 0.18:1:0.09. the resulting catalyst was A6, and the composition and surface roughness data are shown in Table 1.
Preparation example 7
According to the method in preparation example 1, except that Cu (NO 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Ga(NO 3 ) 3 ·xH 2 The molar ratio of O is 0.15:1:0.05. the resulting catalyst was A7 and the composition and surface roughness data are shown in Table 1.
Comparative preparation example 1
According to the method in preparation example 1, except that Ga (NO 3 ) 3 ·xH 2 O. The obtained catalyst was DA1, and the composition and surface roughness data are shown in Table 1.
Comparative preparation example 2
According to the method in preparation example 1, except that Cu (NO 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Ga(NO 3 ) 3 ·xH 2 The molar ratio of O is 0.20:1:0.01. the catalyst adsorbent obtained was DA2, and the composition and surface roughness data are shown in Table 1.
Comparative preparation example 3
The procedure of preparation 1 was followed except that the drying temperature was 210℃and DA3 was used as the catalyst adsorbent, and the composition and surface roughness data are shown in Table 1.
TABLE 1
The following examples are presented to illustrate the process of steam reforming methanol to produce hydrogen.
Example 1
The catalyst adsorbent A1 is filled in a fixed bed reactor, and the molar ratio of water to methanol is 3:1 are mixed into raw materials, vaporized and sent into a fixed bed reactor, and the raw materials are heated to 200 ℃ and the pressure is 0.10MPa, and the methanol volume space velocity is 400h 1 The reaction was carried out under the conditions of (2) and the product was analyzed by chromatography, and the reaction results are shown in Table 2.
Catalytic adsorbent for adsorbing CO 2 After saturation, regenerating the catalytic adsorbent, and introducing the following materials in a volume ratio of 20:1, the volume space velocity of the mixed gas of the carbon dioxide and the oxygen is 500h -1 Regeneration was performed at 320 ℃, noted as a complete regeneration process.
Then cooling, introducing water and methanol again, repeating the reaction and the regeneration process, calculating the conversion rate of methanol and the selectivity of the product after each regeneration, examining the stability, and recycling for 20 times, wherein the results are shown in Table 3.
The energy distribution of the methanol reforming hydrogen production stage and the catalytic adsorbent regeneration stage was calculated using Aspen Plus system flow simulation software, and the reactor heat load is shown in fig. 3 and 4. The catalytic adsorbent provided by the invention can realize self-heating operation of a methanol hydrogen production stage and a regeneration stage, and the heat load is more than 0.
Examples 2 to 7
The procedure of example 1 was followed except that catalytic adsorbents A2 to A7 were used in place of A1, and the product obtained by the reforming reaction was analyzed by chromatography, and the reaction results are shown in Table 2. The results after 20 cycles are shown in Table 3.
Example 8
The procedure of example 1 was followed, except that the molar ratio of water to methanol was 2.5:1. the product obtained by the reforming reaction was analyzed by chromatography, and the reaction results are shown in Table 2. The results after 20 cycles are shown in Table 3.
Example 9
The procedure of example 1 was followed, except that the volume ratio of carbon dioxide to oxygen during regeneration was 10:1, the product obtained by reforming reaction is analyzed by chromatography, and the reaction results are shown in Table 2. The results after 20 cycles are shown in Table 3.
Comparative example 1
Filling the catalyst adsorbent A1 into a fixed bed reactor, and introducing H before reforming reaction 2 N with a volume concentration of 20% 2 And H 2 Reducing the active component Cu in the catalytic adsorbent A1 at 250 ℃; then water and methanol are mixed according to a mole ratio of 3:1 are mixed into raw materials, vaporized and sent into a fixed bed reactor, and the raw materials are heated to 200 ℃ and the pressure is 0.10MPa, and the methanol volume space velocity is 500h 1 The reaction was carried out under the conditions of (2) and the product was analyzed by chromatography, and the reaction results are shown in Table 2.
Catalytic adsorbent for adsorbing CO 2 After saturation, regenerating the catalyst adsorbent in N atmosphere 2 ，N 2 Volume space velocity of 800h -1 Regeneration was performed at 360 ℃, noted as a complete regeneration process. The results after 20 cycles are shown in Table 3.
Comparative example 2
The procedure of example 1 was followed except that the catalytic adsorbent DA1 was used in place of A1, and the product obtained by the reforming reaction was analyzed by chromatography, and the reaction results are shown in Table 2. The results after 7 cycles are shown in Table 3.
Comparative example 3
The procedure of example 1 was followed except that the catalytic adsorbent DA2 was used in place of A1, and the product obtained by the reforming reaction was analyzed by chromatography, and the reaction results are shown in Table 2. The results after 20 cycles are shown in Table 3.
Comparative example 4
The procedure of example 1 was followed except that the catalytic adsorbent DA3 was used in place of A1, and the product obtained by the reforming reaction was analyzed by chromatography, and the reaction results are shown in Table 2. The results after 20 cycles are shown in Table 3.
TABLE 2
TABLE 3 Table 3
As can be seen from the results in table 1, the catalytic adsorbent obtained by the preparation method provided by the invention has proper surface roughness, and further by combining the results in table 2 and table 3, a rich spike-shaped protrusion structure is formed on the surface through the regulation and control of the surface roughness of the catalyst, so that the high dispersion of the reactive sites is promoted; can improve the property and distribution of the alkaline sites on the surface of the catalyst and promote CO 2 Adsorption capacity and improved adsorption and desorption characteristics, thereby reducing regeneration temperature and improving the cycle stability of the catalytic adsorbent.
From the results shown in fig. 3 and fig. 4, it can be seen that the method for preparing hydrogen by reforming methanol steam provided by the invention can realize self-heating operation of the whole reaction by balancing heat absorption and release of oxidation-reduction reaction in the oxidation-steam self-heating reforming and regeneration stages of methanol, reduce energy loss in the reaction process, and improve the engineering application feasibility of the adsorption-enhanced methanol steam reforming technology for preparing high-purity hydrogen.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. A catalytic adsorbent is characterized in that the catalytic adsorbent comprises CuO as a component x -MgO-Ga 2 O 3 Is a composite material of (a); wherein x is more than 0 and less than or equal to 1;
based on the total amount of the catalytic adsorbent, cuO is calculated as CuO x The content of (2) is 10-20wt%, the content of MgO is 70-74wt%, and Ga 2 O 3 The content of (2) is 10-20wt%;
wherein the surface roughness of the catalytic adsorbent is 1-4/mu m 2 。
2. The catalytic adsorbent of claim 1, wherein the catalytic adsorbent has a surface roughness of 1.5-3/μm 2 。
3. The catalytic adsorbent according to claim 1 or 2, wherein CuO, in terms of CuO, is based on the total amount of the catalytic adsorbent x The content of (2) is 11-17wt%, the content of MgO is 70-73wt%, and Ga 2 O 3 The content of (2) is 12-17wt%;
preferably, in the catalytic adsorbent, cuO in elemental form x 、MgO、Ga 2 O 3 The molar ratio of (1) is (0.07-0.18): 1: (0.07-0.09), preferably (0.1-0.16): 1: (0.08-0.09).
4. A method for preparing a catalytic adsorbent, comprising the steps of:
(1) Mixing a Cu source, a Mg source, a Ga source, a gel auxiliary agent and water to obtain a mixed solution;
(2) Under the stirring condition, carrying out gelation reaction on the mixed solution, and then carrying out heat treatment on a product obtained by the reaction;
wherein the Cu source, the Mg source and the Ga source are used in such an amount that CuO is calculated as CuO based on the total amount of the catalyst adsorbent x The content of (2) is 10-20wt%, the content of MgO is 70-74wt%, and Ga 2 O 3 The content of (C) is 10-20wt%.
5. The process according to claim 4, wherein the Cu source, the Mg source and the Ga source are used in such an amount that CuO is calculated as CuO based on the total amount of the catalyst adsorbent x The content of (2) is 11-17wt%, the content of MgO is 70-73wt%, and Ga 2 O 3 The content of (2) is 12-17wt%;
preferably, the molar ratio of Cu source, mg source and Ga source is (0.07-0.18) on an elemental basis: 1: (0.07-0.09), preferably (0.1-0.16): 1: (0.08-0.09).
6. The production method according to claim 4 or 5, wherein the total concentration of the Cu source, mg source and Ga source in the mixed liquid is 0.5 to 2mol/L, preferably 0.8 to 1.2mol/L, in terms of metal element;
the ratio of the molar amount of the gel auxiliary agent to the total molar amount of the Cu source, the Mg source and the Ga source calculated as metal elements is 1-2:1, preferably 1.1-1.5:1.
7. the production method according to any one of claims 4 to 6, wherein the Cu source, mg source and Ga source are each independently selected from soluble salts of metals selected from inorganic salts and/or organic matters;
preferably, the Cu source, mg source and Ga source are each independently selected from at least one of nitrate, acetate and chloride of a metal;
preferably, the gel aid is selected from at least one of citric acid, glucose, polyethylene glycol, ethylene glycol and starch, more preferably citric acid and/or glucose.
8. The preparation method according to any one of claims 4 to 7, wherein the stirring speed is 100 to 1500rpm, further preferably 300 to 800rpm;
preferably, the temperature of the gelation reaction is 30 to 90 ℃, further preferably 60 to 80 ℃;
preferably, the heat treatment comprises: drying and roasting the product obtained by the reaction;
preferably, the drying conditions include: the drying temperature is 130-200deg.C, preferably 150-170deg.C, and the drying time is 5-16h, preferably 10-12h;
preferably, the firing includes: heating to 300-500 ℃ at a heating rate of 1-3 ℃/min, and then roasting at the temperature for 1-10h.
9. A catalytic adsorbent prepared by the method of any one of claims 4-8.
10. A method for producing hydrogen by steam reforming of methanol, the method comprising: under the condition of reforming methanol steam, contacting the methanol steam with a catalytic adsorbent to obtain hydrogen and CO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein CO 2 The catalytic adsorbent is used for adsorption to realize in-situ removal;
the catalytic adsorbent is the catalytic adsorbent of any one of claims 1-3 and 9;
preferably, the catalytic adsorbent is not subjected to reductive activation prior to use.
11. The process of claim 10, the methanol steam reforming reaction being carried out in a fixed bed reactor;
preferably, the methanol steam reforming conditions include: the molar ratio of water to methanol is 1.2-4:1, preferably 2-3:1, a step of; the volume space velocity of the methanol is 200-800h -1 Preferably 300-600h -1 The reaction temperature is 180-240 ℃, preferably 190-220 ℃; the reaction pressure is 0.1-0.2MPa, preferably 0.1-0.15MPa.
12. The method of claim 10 or 11, wherein the method further comprises regenerating the reacted catalytic adsorbent;
preferably, the regenerating comprises: in-situ regenerating the catalytic adsorbent in an oxygen-containing atmosphere;
preferably, the conditions of the regeneration include: the regeneration temperature is 300-400 ℃, preferably 320-360 ℃; the volume space velocity of the oxygen-containing atmosphere is 200-500h -1 Preferably 300-400h -1 ；
Preferably, the oxygen-containing atmosphere is CO 2 With O 2 Wherein CO is 2 And O 2 The volume ratio of (2) is 8-20:1, further preferably 12-20:1.
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