CN101444739A - Copper-based nano-catalyst for hydrogen production by ethanol steam reforming and preparation method thereof - Google Patents
Copper-based nano-catalyst for hydrogen production by ethanol steam reforming and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a copper-based nano-catalyst for hydrogen production by ethanol steam reforming and a preparation method thereof. The catalyst is made by taking nanoporous silicon dioxide aerogel as a catalyst carrier, copper nanowire as an active component, and Al2O3 or ZnO or CeO2 or compound thereof as an adjuvant. The preparation method comprises the following steps: preparing a sol from silanolate, an alcohol solvent, copper nitrate, aluminum nitrate or zinc nitrate or cerous nitrate or complex nitrate thereof and an acidic catalyst at certain proportions; forming a wet gel complex, and then performing supercritical fluid drying. The catalyst has a unique nanoporous structure with high specific area, high porosity, strong catalytic activity and selectivity for the hydrogen production by the ethanol steam reforming, higher hydrogen yield and stronger CO2 selectivity at a lower temperature, and limits the selectivity of byproducts CH4 and CO at a lower level. Meanwhile, the preparation method has simple process, low cost and certain mechanical strength.
Description
Technical field
The invention belongs to liquid fuel for fuel cell hydrogen production by ethanol steam reforming catalyst material technical field, relate to a kind of hydrogen production by ethanol steam reforming Catalysts and its preparation method, especially relating to a kind of is the copper-based nano-catalyst and preparation method thereof of catalyst carrier with the aerosil.
Background technology
The chemical energy that fuel cell directly will be stored in fuel and the oxidant is transformed into electric energy efficiently.High-purity, nontoxic hydrogen is the ideal fuels of fuel cell.At present, the liquid fuel reformation is a kind of hydrogen manufacturing mode preferably.
Ethanol is a kind of renewable resource, and is nontoxic, do not contain the sulphur that the fuel cell platinum electrode is poisoned, and is the environment-friendly type fuel that is fit to hydrogen manufacturing.Ethanol steam reforming is the important channel of ethanol hydrogen production.But the ethanol steam reforming reaction system is complicated, and contingent side reaction has ethanol dehydration, alcohol dehydrogenase, ethanol decomposition, Water gas shift/WGS and CO and CO
2Hydrogenation etc.
Yet, in hydrogen production by ethanol steam reforming technology, how to select and prepare one of key problem in technology that a kind of catalyst of hydrogen production by ethanol steam reforming efficiently is.Up to now, the catalyst that relates to ethanol steam reforming is mainly: noble metal catalyst (as Rh, Pt, Ru and Pd) and non-precious metal catalyst (as Ni, Co and Cu) and oxide catalyst.Wherein the precious metal catalyst has better catalytic effect.In the precious metal catalyst, Rh has better activity and selectivity than other noble metal under identical loading, and the performance of catalyst significantly improves with the increase of loading, and in addition, such catalyst also has good stable.But noble metal cost height, the content in catalyst are often up to 5%, and stability still remains further to be improved.
Oxide catalyst (as MgO, Al
2O
3, V
2O
5, ZnO, TiO
2, La
2O
3, CeO
2, Sm
2O
3, La
2O
3-Al
2O
3, CeO
2-Al
2O
3And MgO-Al
2O
3Deng) have catalytic activity preferably, with low cost, but combination property especially stability is still not good, as Al
2O
3And V
2O
5Active fine, but selectivity is not good enough, ZnO has high activity and selectivity preferably to ethanol steam reforming, but stable bad.
Non-precious metal catalyst is considered to one of very promising ethanol steam reforming catalyst.Such catalyst has high ethanol conversion and hydrogen manufacturing effect, but because catalyst carrier Al
2O
3Acidity cause the catalyst carbon deposit phenomenon more serious, less stable.In addition, CH on nickel-base catalyst
4Relative more with the growing amount of CO, CH
4Competition hydrogen atom, CO are poisoned the Pt electrode of fuel cell, and the two all is not wish the accessory substance that obtains.Though and cobalt-base catalyst has higher selectivity, easy inactivation, the problem of its existence is a poor stability.
In addition, main at present employing infusion process and coprecipitation prepare non-precious metal catalyst, though preparation technology is simple, be difficult to obtain high-specific surface area, high degree of dispersion and homodisperse catalyst, cause the catalytic activity of ethanol steam reforming reaction not high.
Summary of the invention
The object of the present invention is to provide a kind of be catalyst carrier with the aerosil, have an ethanol steam reforming catalytic activity and optionally copper-based nano-catalyst and preparation method thereof preferably.
Aerosil has the feature of high-specific surface area, extremely-low density and nanoporous network structure, is considered to desirable catalyst carrier material.
The objective of the invention is to be achieved through the following technical solutions:
A kind of hydrogen production by ethanol steam reforming copper-based catalysts is a carrier with the nanoporous silica aeroge, and described catalyst is an active component with metal simple-substance copper, with Al
2O
3, ZnO, CeO
2In one or more be auxiliary agent, the form of described metal simple-substance copper is an one-dimensional nano line, described auxiliary agent form is a nano particle, the two all is scattered on the aerosil three-dimensional network skeleton equably with high dispersing mode.
The diameter of the one-dimensional nano line that described metal simple-substance copper forms is 1～5nm, and length is 10～100nm.
The diameter of the nano particle that described auxiliary agent forms is 10～50nm.
The preparation method of described hydrogen production by ethanol steam reforming copper-based catalysts comprises the steps: that (1) adopt two-step method preparation containing metal copper silicon gel: at first with in aluminum nitrate, zinc nitrate, the cerous nitrate one or more with copper nitrate and ethylene glycol solvent mixing and stirring after, under mechanical magnetic agitation and heating condition and acidic catalyst effect, synthesize containing metal copper ethylene glycol; Again containing metal copper ethylene glycol and silicon alkoxide are mixed the Ludox wet gel complex that original position forms containing metal copper under magnetic agitation and heating condition; (2) contain the Ludox wet gel complex of metallic copper by supercritical fluid drying, promptly obtain the aerosil catalyst of containing metal elemental copper nano wire.
Described silicon alkoxide is ethyl orthosilicate or methyl silicate; Described acidic catalyst is acetic acid, hydrofluoric acid, hydrochloric acid or phosphoric acid.
Described silicon alkoxide is an ethyl orthosilicate; Described acidic catalyst is the phosphoric acid best results.
After in described aluminum nitrate, zinc nitrate, the cerous nitrate one or more and the copper nitrate addition and the mol ratio of silicon alkoxide, ethylene glycol, acidic catalyst be 0.06～1:1:2～6:0.08～0.2.
Preferred molar ratio with silicon alkoxide, ethylene glycol, acidic catalyst after described copper nitrate, aluminum nitrate and the cerous nitrate three addition is 0.25～0.3:1:3～4:0.1; Preferred molar ratio with silicon alkoxide, ethylene glycol, acidic catalyst after described copper nitrate, zinc nitrate and the cerous nitrate three addition is 0.5～0.75:1:3:0.1～0.12.
The mol ratio of described copper nitrate, aluminum nitrate and cerous nitrate is 4～8:1～3:1; The mol ratio of described copper nitrate, zinc nitrate and cerous nitrate is 4～8:1～3:1～2.
After one or more and copper nitrate and ethylene glycol solvent mixing and stirring in aluminum nitrate, zinc nitrate, the cerous nitrate, under mechanical magnetic agitation and 85～100 ℃ of heating conditions and acidic catalyst effect, act on 9～12 hours, synthetic containing metal copper ethylene glycol.
Described supercritical fluid drying process, its drying medium is ethanol or isopropyl alcohol, the wet silicon gel complex that will contain metallic copper is put into supercritical fluid drying equipment, the nitrogen of preliminary filling 2～4MPa, be heated to 260～300 ℃ with 50～100 ℃/hour programming rate again, be incubated 1～2 hour, with 1～4MPa/ hour the slow release pressure of speed, dash with nitrogen at last and swept 10～30 minutes again.
The bulk density of described nanoporous silica aeroge is lower than 100kg/m
3
Advantage of the present invention:
(1) this copper-based nano-catalyst, the porosity height, specific area is big, the aperture is suitable, has high catalytic activity and selectivity;
(2) utilize the form of the metal simple-substance copper activity component that in-situ reaction prepares to be one-dimensional nano line, this nanowire diameter is 1～5nm, length is 10～100nm, the adjuvant component form is a nano particle, they are scattered in the aerosil carrier equably with high dispersing mode, not only have high catalytic activity and selectivity, but also improved the mechanical strength of aerosil carrier;
(3) in this copper-based nano-catalyst, the catalytic active component (nano wire) and adjuvant component (nano particle) the content height that utilize original position to form can be adjusted in 0.5～30%wt scope;
(4) in this copper-based nano-catalyst, interact by the generation between nano Ce O particle auxiliary agent and the active component, and the structure of regulation activity component, having improved storage, oxygen release function, the oxidation that helps carbon deposit is eliminated, and improves the anti-deactivation of catalyst;
(5) in this copper-based nano-catalyst,, have high stability, obtained high catalytic activity and selectivity, improved activation stability simultaneously because the ZnO nano particle is evenly dispersed on the aerosil three-dimensional network skeleton;
(6) this copper-based nano-catalyst not only has good catalytic activity, anti-deactivation and stability, and technology is simple, and cost is low.
Description of drawings
Fig. 1 is the TEM photo of typical Nano line of metal copper catalyst.
The specific embodiment
The invention will be further described by the following examples, but protection domain is not subjected to the restriction of these embodiment.
Embodiment 1
With nitrate (mol ratio of copper nitrate, aluminum nitrate and cerous nitrate is 4:1:1), ethyl orthosilicate, ethylene glycol, phosphoric acid in molar ratio 0.25:1:3:0.10 be made into the silicon metal gel with two-step method.Be raw material at first, under magnetic agitation and 90 ℃ of heating conditions, through synthetic containing metal ethylene glycol after 9 hours with mixed nitrate (copper nitrate, aluminum nitrate and cerous nitrate) and ethylene glycol solvent; Then containing metal ethylene glycol and silicon alkoxide are formed silicon metal colloidal sol in magnetic agitation and 90 ℃ of heating 9h original positions; Wore out 3 days down in 60 ℃, put into autoclave, preliminary filling N
2To 3.0MPa, be medium with the isopropyl alcohol, be heated to 250 ℃ with the programming rate of 60 ℃/h, constant temperature kept temperature-resistant after 1 hour, with the slow release pressure of speed of 3MPa/h, to the normal pressure with N
2Dash and swept autoclave 30 minutes, powered-down cools off it naturally, can make copper-based nano-catalyst for hydrogen production by ethanol steam reforming, and metallic copper active component form is an one-dimensional nano line, and diameter is 1～5nm, and length is 10～50nm, Al
2O
3And CeO
2Form be nano particle, be of a size of 10～50nm, it is scattered in the aerosil carrier equably.The TEM photo of typical Nano line of metal copper catalyst is seen Fig. 1.
Catalyst carries out in atmospheric fixed bed continuous flow reactor system the hydrogen production by ethanol steam reforming activity rating, and catalyst amount is 0.2g.Earlier with 5%H
2/ Ar mist is by reactor, and flow-control is at 70ml/min, temperature programming to 650 ℃ reduction activation catalyst 2h, then the reacting furnace temperature is dropped to the setting reaction temperature, switch Ar gas, transfer flow 25ml/min, Ar gas is introduced reaction system with the mixed liquor of water and ethanol and is begun reaction.Be reflected at design temperature and stablize and begin sampling behind the 2h, aerogenesis is through the condenser cooling, and tail gas enters the gas chromatograph on-line analysis after through the six-way valve sampling, and thermal conductivity detector (TCD) detects, and handles with the work station control sampling process line data of going forward side by side.Evaluation result shows: at normal pressure, and 450 ℃ of low temperature, water/ethanol mol ratio=1.1/1.0, WHSV=3.60h
-1Reaction condition under, ethanol conversion is 90.1%, the hydrogen productive rate is 0.326, hydrogen selective is 99.8%, CO
2Selectivity is 99.7%, and CO content is 0.13% in the reformation aerogenesis.
Embodiment 2
With nitrate (mol ratio of copper nitrate, aluminum nitrate and cerous nitrate is 8:2:1), ethyl orthosilicate, ethylene glycol, phosphoric acid in molar ratio 0.25:1:3:0.10 be made into the silicon metal gel with two-step method.With mixed nitrate (copper nitrate, aluminum nitrate and cerous nitrate) and ethylene glycol solvent is raw material, under magnetic agitation and 90 ℃ of heating conditions, through synthetic containing metal ethylene glycol after 9 hours; Then containing metal ethylene glycol and silicon alkoxide are formed silicon metal colloidal sol in magnetic agitation and 90 ℃ of heating 9h original positions; In 60 ℃ aging 3 days down, carry out supercritical drying according to the silicon metal wet gel of 1 pair of acquisition of embodiment and handle, can make copper-based nano-catalyst for hydrogen production by ethanol steam reforming, metallic copper active component form is an one-dimensional nano line, diameter is 1～5nm, and length is 10～50nm, Al
2O
3And CeO
2Form be nano particle, be of a size of 10～50nm, it is scattered in the aerosil carrier equably.
Catalyst activity is estimated with embodiment 1, and evaluation result shows: at normal pressure, and 450 ℃ of low temperature, water/ethanol mol ratio=1.1/1.0, WHSV=3.60h
-1Reaction condition under, ethanol conversion is 93.1%, the hydrogen productive rate is 0.312, hydrogen selective is 99.9%, CO
2Selectivity is 99.4%, and CO content is 0.14% in the reformation aerogenesis.
Embodiment 3
With nitrate (mol ratio of copper nitrate, aluminum nitrate and cerous nitrate is 8:3:1), ethyl orthosilicate, ethylene glycol, phosphoric acid in molar ratio 0.30:1:4:0.10 be made into the silicon metal gel with two-step method.With mixed nitrate (copper nitrate, aluminum nitrate and cerous nitrate) and ethylene glycol solvent is raw material, under magnetic agitation and 90 ℃ of heating conditions, through synthetic containing metal ethylene glycol after 9 hours; Then containing metal ethylene glycol and silicon alkoxide are formed silicon metal colloidal sol in magnetic agitation and 90 ℃ of heating 9h original positions; In 60 ℃ aging 3 days down, carry out supercritical drying according to the silicon metal wet gel of 1 pair of acquisition of embodiment and handle, can make copper-based nano-catalyst for hydrogen production by ethanol steam reforming, metallic copper active component form is an one-dimensional nano line, diameter is 1～5nm, and length is 10～50nm, Al
2O
3And CeO
2Form be nano particle, be of a size of 10～50nm, it is scattered in the aerosil carrier equably.
Catalyst activity is estimated with embodiment 1, and evaluation result shows: at normal pressure, and 450 ℃ of low temperature, water/ethanol mol ratio=1.1/1.0, WHSV=3.60h
-1Reaction condition under, ethanol conversion is 92.6%, the hydrogen productive rate is 0.314, hydrogen selective is 97.7%, CO
2Selectivity is 98.9%, and CO content is 0.15% in the reformation aerogenesis.
Embodiment 4
With nitrate (mol ratio of copper nitrate, aluminum nitrate and cerous nitrate is 8:2:2), ethyl orthosilicate, ethylene glycol, phosphoric acid in molar ratio 0.25:1:3:0.10 be made into the silicon metal gel with two-step method.With mixed nitrate (copper nitrate, aluminum nitrate and cerous nitrate) and ethylene glycol solvent is raw material, under magnetic agitation and 90 ℃ of heating conditions, through synthetic containing metal ethylene glycol after 9 hours; Then containing metal ethylene glycol and silicon alkoxide are formed silicon metal colloidal sol in magnetic agitation and 90 ℃ of heating 9h original positions; In 60 ℃ aging 3 days down, carry out supercritical drying according to the silicon metal wet gel of 1 pair of acquisition of embodiment and handle, can make copper-based nano-catalyst for hydrogen production by ethanol steam reforming, metallic copper active component form is an one-dimensional nano line, diameter is 1～5nm, and length is 10～50nm, Al
2O
3And CeO
2Form be nano particle, be of a size of 10～50nm, it is scattered in the aerosil carrier equably.
Catalyst activity is estimated with embodiment 1, and evaluation result shows: at normal pressure, and 450 ℃ of low temperature, water/ethanol mol ratio=1.1/1.0, WHSV=3.60h
-1Reaction condition under, ethanol conversion is 92.6%, the hydrogen productive rate is 0.316, hydrogen selective is 98.7%, CO
2Selectivity is 99.4%, and CO content is 0.11% in the reformation aerogenesis.
Embodiment 5
With nitrate (mol ratio of copper nitrate, zinc nitrate and cerous nitrate is 4:1:1), ethyl orthosilicate, ethylene glycol, phosphoric acid in molar ratio 0.50:1:3:0.10 be made into the silicon metal gel with two-step method.With mixed nitrate (copper nitrate, zinc nitrate and cerous nitrate) and ethylene glycol solvent is raw material, under magnetic agitation and 100 ℃ of heating conditions, through synthetic containing metal ethylene glycol after 10 hours; Then containing metal ethylene glycol and silicon alkoxide are formed silicon metal colloidal sol in magnetic agitation and 90 ℃ of heating 9h original positions; In 60 ℃ aging 3 days down, carry out supercritical drying according to the silicon metal wet gel of 1 pair of acquisition of embodiment and handle, can make copper-based nano-catalyst for hydrogen production by ethanol steam reforming, metallic copper active component form is an one-dimensional nano line, diameter is 1～5nm, and length is 10～50nm, ZnO and CeO
2Form be nano particle, be of a size of 10～50nm, it is scattered in the aerosil carrier equably.
Catalyst activity is estimated with embodiment 1, and evaluation result shows: at normal pressure, and 450 ℃ of low temperature, water/ethanol mol ratio=1.1/1.0, WHSV=3.60h
-1Reaction condition under, ethanol conversion is 92.6%, the hydrogen productive rate is 0.314, hydrogen selective is 99.3%, CO
2Selectivity is 99.5%, and CO content is 0.14% in the reformation aerogenesis.
Embodiment 6
With nitrate (mol ratio of copper nitrate, zinc nitrate and cerous nitrate is 8:2:1), ethyl orthosilicate, ethylene glycol, phosphoric acid in molar ratio 0.75:1:3:0.12 be made into the silicon metal gel with two-step method.With mixed nitrate (copper nitrate, zinc nitrate and cerous nitrate) and ethylene glycol solvent is raw material, under magnetic agitation and 90 ℃ of heating conditions, through synthetic containing metal ethylene glycol after 12 hours; Then containing metal ethylene glycol and silicon alkoxide are formed silicon metal colloidal sol in magnetic agitation and 90 ℃ of heating 9h original positions; In 60 ℃ aging 3 days down, carry out supercritical drying according to the silicon metal wet gel of 1 pair of acquisition of embodiment and handle, can make copper-based nano-catalyst for hydrogen production by ethanol steam reforming, metallic copper active component form is an one-dimensional nano line, diameter is 1～5nm, and length is 10～50nm, ZnO and CeO
2Form be nano particle, be of a size of 10～50nm, it is scattered in the aerosil carrier equably.
Catalyst activity is estimated with embodiment 1, and evaluation result shows: at normal pressure, and 450 ℃ of low temperature, water/ethanol mol ratio=1.1/1.0, WHSV=3.60h
-1Reaction condition under, ethanol conversion is 92.9%, the hydrogen productive rate is 0.321, hydrogen selective is 99.4%, CO
2Selectivity is 99.1%, and CO content is 0.16% in the reformation aerogenesis.
Embodiment 7
With nitrate (mol ratio of copper nitrate, zinc nitrate and cerous nitrate is 8:3:2), ethyl orthosilicate, ethylene glycol, phosphoric acid in molar ratio 0.75:1:3:0.12 be made into the silicon metal gel with two-step method.With mixed nitrate (copper nitrate, zinc nitrate and cerous nitrate) and ethylene glycol solvent is raw material, under magnetic agitation and 90 ℃ of heating conditions, through synthetic containing metal ethylene glycol after 9 hours; Then containing metal ethylene glycol and silicon alkoxide are formed silicon metal colloidal sol in magnetic agitation and 90 ℃ of heating 9h original positions; In 60 ℃ aging 3 days down, carry out supercritical drying according to the silicon metal wet gel of 1 pair of acquisition of embodiment and handle, can make copper-based nano-catalyst for hydrogen production by ethanol steam reforming, metallic copper active component form is an one-dimensional nano line, diameter is 1～5nm, and length is 10～50nm, ZnO and CeO
2Form be nano particle, be of a size of 10～50nm, it is scattered in the aerosil carrier equably.
Catalyst activity is estimated with embodiment 1, and evaluation result shows: at normal pressure, and 450 ℃ of low temperature, water/ethanol mol ratio=1.1/1.0, WHSV=3.60h
-1Reaction condition under, ethanol conversion is 93.4%, the hydrogen productive rate is 0.323, hydrogen selective is 99.6%, CO
2Selectivity is 99.4%, and CO content is 0.12% in the reformation aerogenesis.
Embodiment 8
With nitrate (mol ratio of copper nitrate, zinc nitrate and cerous nitrate is 4:1:2), ethyl orthosilicate, ethylene glycol, phosphoric acid in molar ratio 0.75:1:3:0.12 be made into the silicon metal gel with two-step method.With mixed nitrate (copper nitrate, zinc nitrate and cerous nitrate) and ethylene glycol solvent is raw material, under magnetic agitation and 90 ℃ of heating conditions, through synthetic containing metal ethylene glycol after 9 hours; Then containing metal ethylene glycol and silicon alkoxide are formed silicon metal colloidal sol in magnetic agitation and 100 ℃ of heating 12h original positions; In 60 ℃ aging 3 days down, carry out supercritical drying according to the silicon metal wet gel of 1 pair of acquisition of embodiment and handle, can make copper-based nano-catalyst for hydrogen production by ethanol steam reforming, metallic copper active component form is an one-dimensional nano line, diameter is 1～5nm, and length is 10～50nm, ZnO and CeO
2Form be nano particle, be of a size of 10～50nm, it is scattered in the aerosil carrier equably.
Catalyst activity is estimated with embodiment 1, and evaluation result shows: at normal pressure, and 450 ℃ of low temperature, water/ethanol mol ratio=1.1/1.0, WHSV=3.60h
-1Reaction condition under, ethanol conversion is 93.4%, the hydrogen productive rate is 0.323, hydrogen selective is 98.6%, CO
2Selectivity is 98.9%, and CO content is 0.15% in the reformation aerogenesis.
Claims (11)
1, a kind of hydrogen production by ethanol steam reforming copper-based catalysts is a carrier with the nanoporous silica aeroge, it is characterized in that, described catalyst is an active component with metal simple-substance copper, with Al
2O
3, ZnO, CeO
2In one or more be auxiliary agent, the form of described metal simple-substance copper is an one-dimensional nano line, described auxiliary agent form is a nano particle, the two all is scattered on the aerosil three-dimensional network skeleton equably with high dispersing mode.
2, hydrogen production by ethanol steam reforming copper-based catalysts according to claim 1 is characterized in that, the diameter of the one-dimensional nano line that described metal simple-substance copper forms is 1～5nm, and length is 10～100nm.
3, hydrogen production by ethanol steam reforming copper-based catalysts according to claim 1 and 2 is characterized in that, the diameter of the nano particle that described auxiliary agent forms is 10～50nm.
4, the preparation method of the described hydrogen production by ethanol steam reforming copper-based catalysts of claim 1, it is characterized in that, comprise the steps: that (1) adopt two-step method preparation containing metal copper silicon gel: at first with in aluminum nitrate, zinc nitrate, the cerous nitrate one or more with copper nitrate and ethylene glycol solvent mixing and stirring after, under mechanical magnetic agitation and heating condition and acidic catalyst effect, synthesize containing metal copper ethylene glycol; Again containing metal copper ethylene glycol and silicon alkoxide are mixed the Ludox wet gel complex that original position forms containing metal copper under magnetic agitation and heating condition; (2) contain the Ludox wet gel complex of metallic copper by supercritical fluid drying, promptly obtain the aerosil catalyst of containing metal elemental copper nano wire.
5, the preparation method of hydrogen production by ethanol steam reforming copper-based catalysts according to claim 4 is characterized in that, described silicon alkoxide is ethyl orthosilicate or methyl silicate; Described acidic catalyst is acetic acid, hydrofluoric acid, hydrochloric acid or phosphoric acid.
According to the preparation method of claim 4 or 5 described hydrogen production by ethanol steam reforming cobalt-base catalysts, it is characterized in that 6, described silicon alkoxide is an ethyl orthosilicate; Described acidic catalyst is a phosphoric acid.
7, the preparation method of hydrogen production by ethanol steam reforming copper-based catalysts according to claim 4, it is characterized in that, after one or more in described aluminum nitrate, zinc nitrate, the cerous nitrate and the copper nitrate addition and the mol ratio of silicon alkoxide, ethylene glycol, acidic catalyst be 0.06～1:1:2～6:0.08～0.2.
8, according to the preparation method of claim 4 or 7 described hydrogen production by ethanol steam reforming copper-based catalysts, it is characterized in that the mol ratio with silicon alkoxide, ethylene glycol, acidic catalyst after described copper nitrate, aluminum nitrate and the cerous nitrate three addition is 0.25～0.3:1:3～4:0.1; Mol ratio with silicon alkoxide, ethylene glycol, acidic catalyst after described copper nitrate, zinc nitrate and the cerous nitrate three addition is 0.5～0.75:1:3:0.1～0.12.
According to the preparation method of claim 4 or 7 described hydrogen production by ethanol steam reforming copper-based catalysts, it is characterized in that 9, the mol ratio of described copper nitrate, aluminum nitrate and cerous nitrate is 4～8:1～3:1; The mol ratio of described copper nitrate, zinc nitrate and cerous nitrate is 4～8:1～3:1～2.
10, the preparation method of hydrogen production by ethanol steam reforming copper-based catalysts according to claim 4, it is characterized in that, after one or more and copper nitrate and ethylene glycol solvent mixing and stirring in aluminum nitrate, zinc nitrate, the cerous nitrate, under mechanical magnetic agitation and 85～100 ℃ of heating conditions and acidic catalyst effect, act on 9～12 hours, synthetic containing metal copper ethylene glycol.
11, the preparation method of hydrogen production by ethanol steam reforming copper-based catalysts according to claim 4, it is characterized in that, described supercritical fluid drying process, its drying medium is ethanol or isopropyl alcohol, the wet silicon gel complex that will contain metallic copper is put into supercritical fluid drying equipment, the nitrogen of preliminary filling 2～4MPa, be heated to 260～300 ℃ with 50～100 ℃/hour programming rate again, be incubated 1～2 hour, with 1～4MPa/ hour the slow release pressure of speed, dash with nitrogen at last and swept 10～30 minutes again.
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| CN114797857A (en) * | 2022-05-20 | 2022-07-29 | 广东工业大学 | Nanometer flower-shaped copper-based material and preparation method and application thereof |
| CN114797857B (en) * | 2022-05-20 | 2023-11-24 | 广东工业大学 | Nanometer flower-like copper-based material, and preparation method and application thereof |
| CN115845861A (en) * | 2022-11-29 | 2023-03-28 | 广东工业大学 | High-dispersion copper-based catalyst and preparation method and application thereof |
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