CN115582124B - 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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- CN115582124B CN115582124B CN202111014926.2A CN202111014926A CN115582124B CN 115582124 B CN115582124 B CN 115582124B CN 202111014926 A CN202111014926 A CN 202111014926A CN 115582124 B CN115582124 B CN 115582124B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
Abstract
The application belongs to the technical field of catalysts, and particularly relates to a copper-based catalyst and a preparation method and application thereof. The 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 Cu ions are further reduced into an active phase, so that the adsorption and dispersion of Cu ions are enhanced, the stability and the hydrogen production efficiency of the catalyst in the hydrogen production reaction are also remarkably improved, and the hydrogen production efficiency of the catalyst is remarkably higher than that of the existing commercial product; the Cu@CS-LN catalyst is simple in preparation method, can be prepared by stirring and heat treatment, hardly generates CO and methane in the reaction process, is environment-friendly, has low-cost and easy-to-obtain copper metal, large storage amount and low cost, and can be used for large-scale industrialized production.
Description
Technical Field
The application belongs to the technical field of catalysts. More particularly, to a carbon material coated copper-based catalyst, a preparation method and application thereof.
Background
The hydrogen energy is an efficient and clean energy source, 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 through gas, the problems of over high pressure, over large volume and the like exist; the hydrogen production by the liquid fuel has the advantages of low hydrogen storage pressure and high hydrogen storage density, and is widely used. The important link of the hydrogen production by the liquid fuel is the water phase reforming hydrogen production technology, the hydrogen is released from the liquid fuel to be directly used, and a feasible choice is provided for solving the difficult problems of hydrogen energy storage and transportation.
Among them, methanol has the advantages of high hydrogen content (12.5 wt%), mature industry, large scale, low cost, guaranteed raw material supply and small safety problem, and becomes an ideal liquid hydrogen carrier for hydrogen production by alcohol reforming, and methanol hydrogen production also becomes an ideal method for hydrogen production by water phase reforming. The current commercial catalysts for hydrogen production by methanol reforming are mainly commercial platinum-carbon, nickel-based and traditional copper-based catalysts, wherein the platinum-based catalysts have excellent hydrogen production activity, high selectivity, high cost and low reserve; the nickel-based catalyst has low cost and good hydrogen production performance, but has high reaction temperature and poor selectivity of products, and is often doped with other metals; the traditional copper-based catalyst has low cost, easy availability, good selectivity of products and is beneficial to generating high-purity H 2 Is widely used, 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 cannot meet the hydrogen production requirement, and is easy to inactivate at high temperature and needs to be matched 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 application aims to overcome the defects and shortcomings 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 application aims to provide a copper-based catalyst.
It is another object of the present application to provide the use of a copper-based catalyst for the catalytic production of hydrogen.
The above object of the present application is achieved by the following technical scheme:
a method for preparing a copper-based catalyst, comprising the steps of:
s1, dissolving chitosan in an acetic acid aqueous solution, adding enzymolysis lignin and copper salt, uniformly stirring to form sol, and drying to obtain a precursor;
s2, calcining the precursor obtained in the step S1 completely at 300-500 ℃ under the condition of neutral gas atmosphere, grinding the product, and fully reacting under the condition of 200-350 ℃ and reducing gas atmosphere to obtain the catalyst.
Preferably, in step S1, the temperature of 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 present in a molar concentration of copper of from 0.02 to 0.1mmol/ml.
Preferably, in the step S1, the mass ratio of the chitosan, the enzymolysis 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 application also protects the 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 loosely structured carbon material.
The chitosan lignin organic carbon skeleton (CS-LN) has an enclosed 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, more electrons are transited from the carbon skeleton into copper nano particles, so that the effect of reducing the copper ions is achieved, and the hydrogen production of the liquid fuel is facilitated.
Preferably, the copper nano particles account for 43-70% of the total mass of the copper-based catalyst.
Furthermore, the application also provides application of the copper-based catalyst in the field of hydrogen production by organic solvent reforming.
Preferably, the catalytic hydrogen production is catalytic hydrogen production by an organic solvent, and the organic solvent is one or more of methanol, ethanol, formic acid or N, N-dimethylformamide.
The application has the following beneficial effects: compared with the prior art, the 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 Cu ions are further reduced into an active phase, so that not only are the adsorption and dispersion of Cu ions enhanced, but also the stability and the hydrogen production efficiency of the catalyst in the hydrogen production reaction are remarkably improved, and the hydrogen production efficiency of the catalyst is remarkably higher than that of the conventional commercial product; the Cu@CS-LN catalyst is simple in preparation method, can be prepared by stirring and heat treatment, hardly generates CO and methane in the reaction process, is environment-friendly, has low-cost and easy-to-obtain copper metal, large storage amount and low cost, and can be used for large-scale industrialized production.
Drawings
FIG. 1 shows the PXRD patterns of the products of inventive example 1 and comparative example 1.
FIG. 2 is a graph showing the Raman spectra of the products of example 1 and comparative example 1 of the present application.
FIG. 3 is a graph showing XPS spectrum characterization of the products of inventive example 1 and comparative example 2.
FIG. 4 is an SEM electron micrograph and a TEM electron micrograph of the product of example 1 and comparative example 1 of the present application.
FIG. 5 is a graph showing the time-dependent hydrogen production efficiency of the copper-based catalyst methanol reforming hydrogen production in example 1 of the present application.
Detailed Description
The application is further illustrated in the following drawings and specific examples, which are not intended to limit the application in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present application are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
S1, adding 1.13g of acetic acid into 90g of ultrapure water to prepare 90ml of acetic acid aqueous solution with the mass fraction of 1.265wt%, wherein the aqueous solution is marked as A solution; adding 0.95g of industrial chitosan with the deacetylation degree of 89.1% into the solution A, stirring at 80 ℃ to completely dissolve the chitosan, wherein the solution is transparent and light yellow;
s2, dissolving 0.05g of enzymolysis lignin (Long Li enzymolysis lignin of Shandong longevity biotechnology Co., ltd.) in 10ml of ultrapure water, and uniformly stirring to obtain a B solution; 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 a speed of 5 ℃/min under a nitrogen atmosphere, calcining for 2 hours at 300 ℃, and grinding the calcined catalyst to obtain the Cu@CS-LN catalyst. 10mg of Cu@CS-LN is taken and reacted for 2 hours in a hydrogen atmosphere at 350 ℃ to obtain an activated Cu@CS-LN catalyst, and an ICP detection result shows that the copper loading in the prepared Cu@CS-LN is 56.24 weight percent.
Example 2
The difference from example 1 is that: in the step S2, copper nitrate with the amount of 1.5g was added, and the mixture was stirred at 80℃for 12 hours to obtain a green solution, thereby obtaining a Cu@CS-LN catalyst with the copper loading amount of 63.51 wt%.
Example 3
The difference from example 1 is that: the precursor prepared in the step S3 is heated to 500 ℃ at a speed of 5 ℃/min under the nitrogen atmosphere, and is subjected to heat treatment for 2 hours at 500 ℃, and the calcined catalyst is ground 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 (2) adding no copper nitrate in the step (S2), stirring and dissolving chitosan and enzymolysis lignin at 80 ℃ to obtain 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 the ethanol aqueous solution with the mass fraction of 90%, and chitosan and enzymolysis lignin are stirred at normal temperature to prepare a dark brown solution, so as to obtain the Cu/CS-LN catalyst.
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 spectra are shown in FIG. 1: the Cu@CS-LN is characterized by the presence of metals Cu and Cu 2 Characteristic diffraction peaks of O, the main three diffraction peaks appear at 43.2 °, 50.4 ° and 74.1 °, respectively, corresponding to lattice planes of (111), (200) and (220) of 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 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 subjected to Raman spectrum analysis, and Raman spectra are shown in fig. 2: CS-LN at 1347cm -1 (D band) and 1583cm -1 There are two distinct characteristic carbon resonances in the (G band), with a higher degree of graphitization (ID/ig=0.82). Cu@CS-LN shows a similar absorption band and ID/IG ratio, whereas in Cu@CS-LN the D band of CS-LN is from 1558cm -1 Up to 1570cm -1 This is probably due to the bonding between the CS-LN and the Cu ions, indicating that the Cu ions have been incorporated into the CS-LN, and electrons of the carbon skeleton CS-LN are transferred to the Cu ions, so that the Cu ions have a lower valence state, and are more favorable for hydrogen production by reforming methanol.
(3) X-ray photoelectron spectroscopy (XPS) analysis
Respectively take outThe products obtained in example 1 and comparative example 2 were subjected to X-ray photoelectron spectroscopy. As shown in fig. 3: analysis of the Cu 2p peak by XPS shows that both Cu@CS-LN and Cu/CS-LN catalysts show metallic Cu/Cu I And Cu II Is a characteristic peak of (2). Cu@CS-LN ratio Cu/CS-LN surface Cu II The binding energy of Cu 2p3/2 and Cu 2p1/2 at much lower levels reduced the charge level of Cu@CS-LN to 932.7 and 952.6eV, respectively, 0.5eV lower than Cu/CS-LN. Because CS-LN has a surrounded 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, more electrons are transited from a carbon skeleton to copper nano particles, the effect of reducing the copper ions is achieved, and the hydrogen production by reforming methanol is facilitated.
(4) Scanning electron microscope (TEM) and Transmission Electron Microscope (TEM) analysis
The products obtained in example 1 and comparative example 1 were subjected to scanning electron microscopy and transmission electron microscopy, respectively. It can be seen from FIGS. 4 (a) and 4 (b) that 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 substrate MeOH/H 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 shows that Cu nanoparticles having an average particle diameter of 12.77.+ -. 2.87nm are present at 4.3X11015/m 2 Is highly uniformly and densely distributed on the amorphous CS-LN framework, measuredThe lattice fringe spacing can be well attributed to the metallic Cu (111) crystal plane, demonstrating successful fabrication of highly dispersed copper nanoparticles.
(5) Comparison of Hydrogen production Performance by methanol reforming with copper-based catalyst in various examples
The copper-based catalysts obtained in examples 1, 2 and 3 were subjected to performance tests in a batch reactor, and the tests were as follows: 10mg of the activated copper-based catalyst was added to 10ml of a mixed solution of methanol, water and potassium hydroxide in a mass ratio of 16:27:2.26, and the mixture was treated with 2MPa N 2 As protective gas, reacting at 190-210 deg.C for 75min, cooling to room temperature, and gas-phase chromatographyQuantitative analysis was performed and the results are shown in table 1.
Table 1 comparison of hydrogen production performance from methanol reforming with copper-based catalysts in different examples
As can be seen from table 1: under the reaction conditions, the hydrogen production content in the methanol reforming hydrogen production in each example is higher than that in the comparative example, the hydrogen production content in the reaction of comparative example 2 is only 8.23% at 210 ℃, the hydrogen production content in the reaction of the examples at 190 ℃ is more than 93%, and the hydrogen production content in the reaction at 210 ℃ is more than 99%; the generated carbon monoxide values are lower than the gas chromatography minimum detection line (< 500 ppm), and the purification treatment of the subsequent gas generated by hydrogen production through methanol liquid phase reforming is simpler than that of methanol steam reforming; examples 1 and 2 produced hydrogen up to 215.33. Mu. Mol H when reacted at 210 ℃ 2 /(s*g)、396.70μmol H 2 /(s*g)。
(6) Comparison of Hydrogen production Performance with copper-based catalyst and commercial catalyst methanol reforming at different temperatures
The copper-based catalysts obtained in example 1 and example 2 were tested for performance with commercial catalysts in batch reactors as follows: 10mg of copper-based catalyst was first reduced at 350℃for 2h at a hydrogen flow rate of 50 mL/min. 10ml of a mixed solution of methanol, water and potassium hydroxide in a mass ratio of 16:27:2.26 is added into the reaction system. At 2MPa N 2 The gas phase product was quantitatively analyzed with a commercial catalyst by using gas chromatography after cooling to room temperature after reacting at 190 to 210℃for 75 minutes as a shielding gas, and the results are shown in Table 2.
TABLE 2 comparison of Hydrogen production Performance of copper-based catalysts and commercial catalysts for methanol reforming at different temperatures
As can be seen from table 2: under the above reaction conditions, the copper-based catalyst of the present application exhibited the best hydrogen production performance activity at a CuOx loading of 63.51% (example 2), and the hydrogen production rate was decreased to various degrees at a CuOx loading of less than or greater than 63.51%. 63.51% of Cu@CS-LN reacts at 210℃with a hydrogen production rate of 296.70. Mu. Mol H 2 /(s.g), 5% Pt/C (107.10. Mu. Mol H) higher than commercial platinum carbon catalyst 2 /(s.g.), far higher than Ranny Ni hydrogen production rate (83.56. Mu. Mol H) under the same conditions 2 /(s*g))。
(7) Stability experiment of copper-based catalyst for methanol reforming Hydrogen production in example 1
Long-term durability tests were performed on a continuous flow fixed bed reactor to evaluate the catalytic stability of the cu@cs-LN catalyst. As can be seen from FIG. 5, no catalyst deactivation was detected after 150 hours of operation, and H was continuously produced 2 Average production rate of 5.6X104. Mu. Mol H 2 gCu -1 h -1 . The morphology of the post-reaction (A.R) Cu@CS-LN catalyst is unchanged, which indicates the structural stability and subsequent catalysis of MeOH/H 2 Stability of hydrogen production by the O reforming system. The copper-based catalyst has high hydrogen production performance and almost no side reaction, and solves the technical problems of low cost, low performance of the easily obtained metal catalyst and high cost of the noble metal catalyst.
The above examples are preferred embodiments of the present application, but the embodiments of the present application are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present application should be made in the equivalent manner, and the embodiments are included in the protection scope of the present application.
Claims (6)
1. The preparation method of the copper-based catalyst for producing hydrogen by catalyzing with an organic solvent is characterized by comprising the following steps:
s1, dissolving chitosan in an acetic acid aqueous solution, adding enzymolysis lignin and copper salt, uniformly stirring to form sol, and drying to obtain a precursor;
s2, calcining the precursor obtained in the step S1 completely under the conditions of 300-500 ℃ and neutral gas atmosphere, grinding the product, and fully reacting under the conditions of 200-350 ℃ and reducing gas atmosphere to obtain the catalyst;
in the step S1, the mass ratio of the chitosan to the enzymatic hydrolysis lignin is 1 (0.05-0.2);
in step S2, the reducing gas is hydrogen;
the organic solvent is methanol;
the copper nano particles account for 43-70% of the total mass of the copper-based catalyst.
2. The method for preparing a copper-based catalyst for the catalytic production of hydrogen by an organic solvent according to claim 1, wherein in step S1, the copper salt is copper nitrate, copper sulfate or copper chloride.
3. The process for preparing the copper-based catalyst for the catalytic production of hydrogen by an organic solvent according to claim 1, characterized in that in step S1, the copper salt is present in an amount of 0.02 to 0.1mmol/ml in terms of molar concentration of copper.
4. The method for preparing a copper-based catalyst for catalytic hydrogen production by an organic solvent according to claim 1, wherein in step S2, the neutral gas is nitrogen or argon.
5. The copper-based catalyst for catalyzing hydrogen production by using an organic solvent, which is prepared by the preparation method according to any one of claims 1 to 4, is characterized in that the copper-based catalyst for catalyzing hydrogen production by using the organic solvent comprises copper nano particles and a carbon carrier, wherein the copper nano particles are uniformly dispersed on a carbon material with loose structure; the copper nano particles account for 43-70% of the total mass of the copper-based catalyst.
6. The use of the copper-based catalyst for the catalytic production of hydrogen with an organic solvent according to claim 5, wherein the organic solvent is methanol.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157473A (en) * | 2013-03-27 | 2013-06-19 | 北京林业大学 | Methanol cracking catalyst and preparation method thereof |
| CN104689857A (en) * | 2015-03-26 | 2015-06-10 | 中国科学院青岛生物能源与过程研究所 | Preparing method for nitrogen-doped porous carbon material, catalyst comprising material and application of material |
| CN109201057A (en) * | 2018-10-12 | 2019-01-15 | 长江师范学院 | A kind of preparation method of lignin-base carbon supported nano-gold category oxide catalyst |
| CN109802124A (en) * | 2019-02-14 | 2019-05-24 | 西南大学 | Metal atom doped porous carbon nano-composite material of one kind and its preparation method and application |
| CN111604028A (en) * | 2020-05-14 | 2020-09-01 | 黑龙江大学 | Preparation method of nitrogen-doped porous biomass carbon |
| CN112047301A (en) * | 2020-09-07 | 2020-12-08 | 广州氢动科技有限公司 | Self-adaptive solar thermal drive methanol liquid-phase reforming hydrogen production device and method |
-
2021
- 2021-08-31 CN CN202111014926.2A patent/CN115582124B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157473A (en) * | 2013-03-27 | 2013-06-19 | 北京林业大学 | Methanol cracking catalyst and preparation method thereof |
| CN104689857A (en) * | 2015-03-26 | 2015-06-10 | 中国科学院青岛生物能源与过程研究所 | Preparing method for nitrogen-doped porous carbon material, catalyst comprising material and application of material |
| CN109201057A (en) * | 2018-10-12 | 2019-01-15 | 长江师范学院 | A kind of preparation method of lignin-base carbon supported nano-gold category oxide catalyst |
| CN109802124A (en) * | 2019-02-14 | 2019-05-24 | 西南大学 | Metal atom doped porous carbon nano-composite material of one kind and its preparation method and application |
| CN111604028A (en) * | 2020-05-14 | 2020-09-01 | 黑龙江大学 | Preparation method of nitrogen-doped porous biomass carbon |
| CN112047301A (en) * | 2020-09-07 | 2020-12-08 | 广州氢动科技有限公司 | Self-adaptive solar thermal drive methanol liquid-phase reforming hydrogen production device and method |
Non-Patent Citations (1)
| Title |
|---|
| 董瑾等."碳球粒径对Cu/C催化剂甲醇水蒸气重整反应性能的影响".《上海应用技术学院学报（自然科学版）》.2016,第16卷(第2期),第132-135页. * |
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