CN115582124A - Copper-based catalyst and preparation method and application thereof - Google Patents
Copper-based catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a copper-based catalyst, and a preparation method and application thereof. Cu ions in the copper-based catalyst Cu @ CS-LN prepared by the method can be uniformly dispersed and loaded in a unique carbon skeleton structure of CS-LN, and are further reduced into an active phase, so that the adsorption and dispersion of the Cu ions are enhanced, the stability and the hydrogen production efficiency in the hydrogen production reaction are remarkably improved, and the hydrogen production efficiency is remarkably higher than that of the conventional commercial product; the preparation method of the Cu @ CS-LN catalyst is simple, the catalyst can be prepared only by stirring and heat treatment, CO and methane are hardly generated in the reaction process, the catalyst is green and environment-friendly, the needed copper metal is cheap and easy to obtain, the reserve amount is large, the cost is low, and the catalyst can be used for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of catalysts. More particularly, relates to a carbon material coated copper-based catalyst, and a preparation method and application thereof.
Background
Hydrogen energy is a high-efficiency clean energy, and has the characteristics of high heat value (up to 1.42 multiplied by 102 MJ/kg), multiple forms and energy storage, so that the hydrogen energy is widely applied to the fields of fuel cells, industrial synthesis, aerospace, energy storage and the like, and becomes an energy source with the prospect of replacing fossil fuels. The popularization of hydrogen energy requires clean and sustainable hydrogen supply, but if hydrogen is directly transported by gas, the problems of over-high pressure, over-large volume and the like exist; the liquid fuel hydrogen production has the advantages of low hydrogen storage pressure and high hydrogen storage density, and is widely used. The important link of liquid fuel hydrogen production is a water-phase reforming hydrogen production technology, hydrogen is released from liquid fuel to be directly used, and a feasible selection is provided for solving the problems of hydrogen energy storage and transportation.
The methanol is an ideal liquid hydrogen carrier for hydrogen production by alcohol reforming because of its high hydrogen content (12.5 wt%), mature industry, large scale, low cost, guaranteed raw material supply and small safety problem, and the hydrogen production by methanol is also an ideal method for hydrogen production by aqueous phase reforming. At present, commercial catalysts for methanol reforming hydrogen production are mainly commercial platinum carbon, nickel-based and traditional copper-based catalysts, wherein the platinum-based catalysts have excellent hydrogen production activity and high selectivity, but have high cost and low storage; the nickel-based catalyst has low cost and good hydrogen production performance, but has high reaction temperature and poor product selectivity, and is often doped with other metals; the traditional copper-based catalyst has the advantages of low price, easy obtaining, good product selectivity and contribution to generating high-purity H 2 For example, chinese patent application CN108554407A discloses a nano copper-based catalyst which has low cost and good catalytic effect, but when copper is used alone, the hydrogen production activity still can not meet the hydrogen production requirement, and the catalyst is easy to inactivate at high temperature and needs to react with SiO 2 The combination and interaction are not strong, and the dispersibility, the stability and the catalytic activity are poor due to easy sintering and agglomeration.
Disclosure of Invention
The invention aims to solve the technical problems of low hydrogen production efficiency, poor dispersibility, poor stability and poor catalytic activity of the catalyst in the existing liquid fuel hydrogen production technology, and provides a preparation method of a copper-based catalyst with high hydrogen production efficiency, good dispersibility, good stability and good catalytic activity.
The invention aims to provide a copper-based catalyst.
The invention also aims to provide the application of the copper-based catalyst in the catalytic hydrogen production.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a copper-based catalyst comprises the following steps:
s1, dissolving chitosan in an acetic acid aqueous solution, adding enzymatic hydrolysis lignin and copper salt, uniformly stirring to form sol, and drying to obtain a precursor;
s2, completely calcining the precursor obtained in the step S1 at the temperature of 300-500 ℃ under the neutral gas atmosphere, grinding the product, and fully reacting at the temperature of 200-350 ℃ under the reducing gas atmosphere to obtain the catalyst.
Preferably, in step S1, the temperature of the dissolution is 60 to 80 ℃.
Preferably, in the step S1, the mass ratio of the chitosan to the enzymatic hydrolysis lignin is 1 (0.05-0.2).
Preferably, in step S1, the acetic acid concentration of the aqueous acetic acid solution is 0.02 to 0.05mol/L.
Preferably, in step S1, the copper salt is copper nitrate, copper sulfate or copper chloride.
Preferably, in step S1, the copper salt is in the range of 0.02 to 0.1mmol/ml in terms of copper molar concentration.
Preferably, in step S1, the mass ratio of the chitosan, the enzymatic hydrolysis lignin, the copper salt and the acetic acid aqueous solution is (0.5-2): 0.05-0.2): 1-4.2): 90-100.
Preferably, in step S1, the drying temperature is 60 to 80 ℃ and the drying time is 5 to 24 hours.
Preferably, in step S2, the neutral gas is nitrogen or argon.
Preferably, in step S2, the calcination time is 2 to 3 hours.
Preferably, in step S2, the reducing gas is hydrogen, CO or methane.
More preferably, in step S2, the reducing gas is hydrogen.
Preferably, in step S2, the reaction time is 2 to 4 hours.
The invention also discloses a copper-based catalyst Cu @ CS-LN prepared by the method.
Preferably, the copper-based catalyst comprises copper nanoparticles and a carbon support, wherein the copper nanoparticles are uniformly dispersed on a carbon material with a loose structure.
The chitosan lignin organic carbon skeleton (CS-LN) has a surrounded pi-rich conjugated structure, and after Cu @ CS-LN is formed by self-assembly, low-valence copper ions are formed, the low-valence copper has higher electron density, and more electrons jump from the carbon skeleton to copper nanoparticles, so that the effect of reducing the copper ions is achieved, and hydrogen production by liquid fuel is facilitated.
Preferably, the copper nanoparticles account for 43-70% of the total mass of the copper-based catalyst.
Further, the invention also provides application of the copper-based catalyst in the field of hydrogen production by reforming an organic solvent.
Preferably, the hydrogen production by catalysis is hydrogen production by catalysis of an organic solvent, and the organic solvent is one or more of methanol, ethanol, formic acid or N, N-dimethylformamide.
The invention has the following beneficial effects: compared with the prior art, the Cu ions in the copper-based catalyst Cu @ CS-LN prepared by the invention can be uniformly dispersed and loaded in the unique carbon skeleton structure of CS-LN, and the Cu ions are further reduced into an active phase, so that the adsorption and dispersion of the Cu ions are enhanced, the stability and the hydrogen production efficiency in the hydrogen production reaction are also obviously improved, and the hydrogen production efficiency is obviously higher than that of the existing commercial product; the preparation method of the Cu @ CS-LN catalyst is simple, the catalyst can be prepared only by stirring and heat treatment, CO and methane are hardly generated in the reaction process, the catalyst is green and environment-friendly, the needed copper metal is cheap and easy to obtain, the reserve amount is large, the cost is low, and the catalyst can be used for large-scale industrial production.
Drawings
FIG. 1 is a PXRD spectrum of the product of example 1 and comparative example 1 of the present application.
FIG. 2 shows Raman spectra of the products of example 1 and comparative example 1 of the present application.
FIG. 3 is an XPS spectrum of the products of example 1 and comparative example 2 of the present application.
FIG. 4 is an SEM electron micrograph and a TEM electron micrograph of the products of example 1 and comparative example 1 of the present application.
Fig. 5 is a graph showing the time-dependent change of the hydrogen production efficiency of methanol reforming, which is a copper-based catalyst in example 1 of the present application.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
S1, adding 1.13g of acetic acid into 90g of ultrapure water, and preparing 90ml of an acetic acid aqueous solution with the mass fraction of 1.265wt%, wherein the acetic acid aqueous solution is marked as solution A; adding 0.95g of chitosan with the deacetylation degree of 89.1% in the solution A, and stirring at 80 ℃ to completely dissolve the chitosan, wherein the solution is transparent and light yellow;
s2, dissolving 0.05g of enzymatic hydrolysis lignin (Longli enzymatic hydrolysis lignin of Shandong Long-lived Biotech Co., ltd.) in 10ml of ultrapure water, and uniformly stirring to mark as liquid B; pouring the solution B into the solution A, uniformly stirring at 80 ℃, adding 0.946g of copper nitrate, heating and stirring for 12 hours to obtain a blue-green solution, drying the solution in a 70 ℃ oven for 12 hours, and grinding the dried sample to obtain a Cu @ CS-LN precursor;
s3, heating the precursor to 300 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, calcining for 2h at 300 ℃, and grinding the calcined catalyst to obtain the Cu @ CS-LN catalyst. Taking 10mg Cu @ CS-LN, reacting for 2h at 350 ℃ in a hydrogen atmosphere to obtain an activated Cu @ CS-LN catalyst, and displaying the load amount of the copper in the prepared Cu @ CS-LN as the result of ICP detection, wherein the load amount of the copper is 56.24wt%.
Example 2
The difference from example 1 is that: in step S2, 1.5g of copper nitrate was added, and the mixture was stirred at 80 ℃ for 12 hours to obtain a green solution, and a Cu @ CS-LN catalyst having a copper loading of 63.51wt% was obtained.
Example 3
The difference from example 1 is that: and (3) heating the precursor prepared in the step (S3) to 500 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, carrying out heat treatment for 2h at 500 ℃, and grinding the calcined catalyst to obtain the Cu @ CS-LN catalyst with the copper loading of 51.95 wt%.
Comparative example 1
The difference from example 1 is that: and (3) in the step (S2), copper nitrate is not added, and the chitosan and the enzymatic hydrolysis lignin are stirred and dissolved at the temperature of 80 ℃ to prepare the CS-LN carbon skeleton.
Comparative example 2
The difference from example 1 is that: in the step S1, the acetic acid aqueous solution with the mass fraction of 1.265wt% is replaced by an ethanol aqueous solution with the mass fraction of 90%, and the chitosan and the enzymatic hydrolysis lignin are stirred at normal temperature to prepare a dark brown solution, so that the Cu/CS-LN catalyst is obtained.
Performance testing
(1) Product X-ray diffraction (PXRD) analysis
The products obtained in example 1 and comparative example 1 were subjected to X-ray diffraction analysis, and the PXRD pattern is shown in fig. 1: the presence of metal Cu and Cu in Cu @ CS-LN 2 The characteristic diffraction peaks of O, the main three appearing at 43.2 °, 50.4 ° and 74.1 °, respectively, correspond to the lattice planes of (111), (200) and (220) of the cubic phase Cu (pd # 85-1326), respectively; peaks at 36.6 °, 42.5 ° and 73.8 °, corresponding to Cu, respectively 2 Lattice planes of (111), (200) and (311) of O (pd # 78-2076). The results show that the highly dispersed and encapsulated Cu ions in CS-LN are almost completely reduced to the active phase after pyrolysis.
(2) Raman spectroscopy (Raman) analysis
The products obtained in example 1 and comparative example 1 were taken for Raman spectroscopy, and the Raman spectra are shown in fig. 2: CS-LN at 1347cm -1 (D band) and 1583cm -1 (G-band) there are two distinct characteristic carbon resonances with a high degree of graphitization (ID/IG = 0.82). Cu @ CS-LN shows similar absorption bands and ID/IG ratios, whereas in Cu @ CS-LN the D band of CS-LN is from 1558cm -1 Rise to 1570cm -1 The bonding effect between CS-LN and Cu ions indicates that the Cu ions are fused into the CS-LN, and electrons of the CS-LN of the carbon skeleton are transferred to the Cu ions, so that the Cu ions have a lower valence state, and the hydrogen production by methanol reforming is facilitated.
(3) X-ray photoelectron spectroscopy (XPS) analysis
The products obtained in example 1 and comparative example 2 were taken for X-ray photoelectron spectroscopy. As shown in fig. 3: analysis of the Cu 2p peak by XPS, both Cu @ -CS-LN and Cu/CS-LN catalysts showed metallic Cu/Cu I And Cu II Characteristic peak of (2). Cu @ CS-LN ratio Cu/CS-LN surface Cu II The content is much lower, and the combination energy of Cu 2p3/2 and Cu 2p1/2 reduces the charge capacity of Cu @ CS-LN to 932.7 and 952.6eV, which are respectively 0.5eV lower than that of Cu/CS-LN. As CS-LN has a surrounding pi-rich conjugated structure, after Cu @ CS-LN is formed by self-assembly, low-valence copper ions are formed, the low-valence copper has higher electron density, and more electrons jump into copper nanoparticles from a carbon skeleton, so that the effect of reducing the copper ions is achieved, and the hydrogen production by reforming methanol is facilitated.
(4) Scanning Electron microscopy (TEM) and Transmission Electron Microscopy (TEM) analysis
The products obtained in example 1 and comparative example 1 were analyzed by scanning electron microscopy and transmission electron microscopy, respectively. As can be seen from FIGS. 4 (a) and 4 (b), the surface of Cu @ CS-LN is significantly rougher than that of CS-LN, and has many micropores and mesopores. The introduction of Cu increases the mesoporous volume, effectively increases the MeOH/H of a substrate around the active site of Cu 2 The concentration of O is more favorable for the adsorption of the substrate. As shown in FIG. 4 (c), TEM image of Cu @ CS-LN showed that Cu nanoparticles having an average particle size of 12.77. + -. 2.87nm were 4.3X 1015/m 2 Is highly uniformly and densely distributed in the amorphous CS-LN frameOn shelf, measured
The lattice fringe spacing can be well attributed to the metallic Cu (111) lattice planes, demonstrating the successful preparation of highly dispersed copper nanoparticles.
(5) Comparison of methanol reforming hydrogen production performance of copper-based catalyst in each example
The copper-based catalysts obtained in examples 1, 2 and 3 were subjected to performance tests in a batch reactor, and the experiments were as follows: 10mg of the activated copper-based catalyst was added to 10ml of a mixed solution of methanol, water and potassium hydroxide at a mass ratio of 16.26, under 2MPa N 2 As a protective gas, the reaction was carried out at 190 to 210 ℃ for 75min, and the gas product was quantitatively analyzed by gas chromatography after cooling to room temperature, the results of which are shown in table 1.
TABLE 1 comparison of methanol reforming hydrogen production performance of copper-based catalyst in different examples
From table 1, it can be seen that: under the reaction conditions, the content of hydrogen generated in the hydrogen production by reforming methanol in each example is higher than that in the comparative example 2, the hydrogen production content is only 8.23% when the reaction is carried out at 210 ℃, the hydrogen production content in the reaction is more than 93% when the reaction is carried out at 190 ℃, and the hydrogen production content in the reaction at 210 ℃ is more than 99%; the generated carbon monoxide values are all lower than the lowest detection line (less than 500 ppm) of a gas chromatograph, and the subsequent gas purification treatment of hydrogen production and gas production by methanol liquid-phase reforming is proved to be simpler than methanol steam reforming; example 1 and example 2 when reacted at 210 ℃ Hydrogen production can reach 215.33. Mu. Mol H 2 /(s*g)、396.70μmol H 2 /(s*g)。
(6) Comparison of methanol reforming hydrogen production performance of copper-based catalyst and commercial catalyst at different temperatures
The copper-based catalysts obtained in examples 1 and 2 were tested with commercial catalysts in a batch reactor for performance, as follows: 10mg of copper-based catalyst is reduced for 2 hours at 350 ℃ under the hydrogen flow rate of 50 mL/min. 10ml of a mixed solution of methanol, water and potassium hydroxide in a mass ratio of 16. At 2MPa N 2 As protective gas, the reaction was carried out at 190-210 ℃ for 75min, and after cooling to room temperature, the gas product and the commercial catalyst were quantitatively analyzed by gas chromatography, the results of which are shown in Table 2.
TABLE 2 comparison of methanol reforming Hydrogen production Performance of copper-based catalysts at different temperatures with commercial catalysts
From table 2, it can be seen that: under the above reaction conditions, the copper-based catalyst of the present invention exhibited the best hydrogen production performance activity when the CuOx loading was 63.51% (example 2), and the hydrogen production rate decreased to various degrees when the CuOx loading was less than or greater than 63.51%. 63.51% Cu @ CS-LN was reacted at 210 ℃ with a hydrogen generation rate of 296.70. Mu. Mol H 2 V (s g), higher than commercial platinum carbon catalyst 5% Pt/C (107.10. Mu. Mol H) 2 /(s. G)), much higher than Ranny Ni hydrogen production rate under the same conditions (83.56. Mu. Mol H) 2 /(s*g))。
(7) Stability experiment for methanol reforming hydrogen production with copper-based catalyst in example 1
A long-term durability test was conducted on a continuous flow fixed bed reactor to evaluate the catalytic stability of a Cu @ CS-LN catalyst. As can be seen from FIG. 5, no catalyst deactivation was detected after 150H of operation and H was continuously produced 2 Average formation rate of 5.6X 104. Mu. Mol H 2 gCu -1 h -1 . After the reaction, (A.R) Cu @ CS-LN catalyst has no change in form, indicating the stability of the structure and the subsequent catalysis of MeOH/H 2 Stability of O reforming system hydrogen production. The copper-based catalyst has high hydrogen production performance and almost no side reaction, and solves the technical problems of poor performance of cheap and easily available metal catalysts and high cost of noble metal catalysts.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the copper-based catalyst is characterized by comprising the following steps of:
s1, dissolving chitosan in an acetic acid aqueous solution, adding enzymatic hydrolysis lignin and copper salt, uniformly stirring to form sol, and drying to obtain a precursor;
s2, completely calcining the precursor obtained in the step S1 at the temperature of 300-500 ℃ under the neutral gas atmosphere condition, grinding the product, and fully reacting at the temperature of 200-350 ℃ under the reducing gas atmosphere condition to obtain the catalyst.
2. The preparation method of the copper-based catalyst according to claim 1, wherein in the step S1, the mass ratio of the chitosan to the enzymatic hydrolysis lignin is 1 (0.05-0.2).
3. The method for preparing the copper-based catalyst according to claim 1, wherein in step S1, the copper salt is copper nitrate, copper sulfate or copper chloride.
4. The process for preparing the copper-based catalyst according to claim 1, wherein the copper salt is 0.02 to 0.1mmol/ml in terms of copper molar concentration in step S1.
5. The method for producing the copper-based catalyst according to claim 1, wherein in step S2, the neutral gas is nitrogen or argon.
6. The method for producing a copper-based catalyst according to claim 1, wherein in step S2, the reducing gas is hydrogen, CO or methane.
7. Copper-based catalyst prepared by the preparation method of any one of claims 1 to 6, characterized in that the copper-based catalyst comprises copper nanoparticles and a carbon carrier, and the copper nanoparticles are uniformly dispersed on a carbon material with a loose structure.
8. Copper-based catalyst according to claim 7, characterized in that the copper nanoparticles represent 43 to 70% of the total mass of the copper-based catalyst.
9. Use of the copper-based catalyst according to claim 7 or 8 for the catalytic production of hydrogen.
10. The application of claim 9, wherein the hydrogen production by catalysis is hydrogen production by catalysis of an organic solvent, and the organic solvent is one or more of methanol, ethanol, formic acid or N, N-dimethylformamide.
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