CN112675874B - For CO 2 Pd-Cu for preparing methanol by catalytic hydrogenation 2 Preparation method of O catalyst - Google Patents
For CO 2 Pd-Cu for preparing methanol by catalytic hydrogenation 2 Preparation method of O catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing CO 2 Pd-Cu for preparing methanol by catalytic hydrogenation 2 The invention discloses a preparation method of an O catalyst, relates to the technical field of catalysts, and firstly utilizes CTAB and H 2 PdCl 4 Reacting with KI in water solution, adding ascorbic acid to prepare mixed solution containing Pd metal particles, and adding CuCl into the mixed solution containing Pd metal particles 2 With alkali liquor to finally prepare Cu 2 Pd-Cu of Yolk structure (Yolk-Shell) of O-coated Pd metal particles 2 An O catalyst; the prepared Yolk structure (Yolk-Shell) Pd-Cu 2 O catalyst, abbreviated as YS-Pd/Cu 2 O, the appearance of the electron microscope image is shown as figure 1, and the yolk structure YS-Pd/Cu 2 O in Cu + Is favorable for weakening surface adsorption of CO 2 C-O bond in (C-O) to form CO, which is further reacted with H 2 The hydrogenation reaction is carried out under the catalysis of Pd to form methanol. In addition, the YS-Pd/Cu provided by the invention 2 O catalyst, using Cu 2 Yolk structure YS-Pd/Cu of O-coated Pd nanoparticles 2 The O catalyst has more stable catalytic performance and longer service life.
Description
Technical Field
The invention relates to the technical field of catalysts for catalytic hydrogenation and quality improvement of biomass, in particular to a catalyst for CO 2 Pd-Cu for preparing methanol by catalytic hydrogenation 2 O catalyst preparation method.
Background
The excessive consumption of fossil fuels raises concerns about environmental issues and national energy safety, and thus, the demand for environmentally friendly and renewable alternative fuels is increasing. At present, CO 2 As a widely-occurring carbon source, it plays an increasingly important role in the chemical industry and is one of promising renewable energy sources. To CO 2 The catalytic hydrogenation is carried out to prepare high value-added chemical products such as methanol and the like, and the economic value is extremely high.
At present, CO 2 The catalytic hydrogenation is carried out to prepare the methanol, and the catalytic reaction is carried out by using a Pd/Cu/Zr ternary active catalyst, such as the patent publication with the publication number of CN109999833A, CN102091618A, but CO 2 The conversion rate of the catalyst is very low and is not higher than 20 percent; pd-Cu 2 O catalysts are currently used mostly for acetylene hydrogenation, as disclosed in patent publication No. CN103977814B, which is used directly for CO 2 The catalytic hydrogenation for preparing methanol can further improve CO 2 The conversion rate of the catalyst is about 60 percent, but the yield of the methanol is less than 25 percent, the catalytic selectivity is low, in addition, the activity of the catalyst is unstable in the using process, the deactivation phenomenon appears shortly after the catalyst is used, and the catalyst needs to be replenished again.
Disclosure of Invention
The invention aims to provide a method for preparing CO 2 Pd-Cu for preparing methanol by catalytic hydrogenation 2 The preparation method of the O catalyst aims to solve the technical problem that the existing catalyst is low in conversion rate and selectivity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
for CO 2 Pd-Cu for preparing methanol by catalytic hydrogenation 2 The preparation method of the O catalyst comprises the following steps:
(1) Completely dissolving CTAB powder in deionized water to obtain a CTAB aqueous solution;
(2) Adding H to the above CTAB aqueous solution 2 PdCl 4 Solution and KI solution, the H 2 PdCl 4 The molar ratio of the solution to KI is 1: 5-1: 8, the solution is stirred uniformly and then transferred into an oil bath at the temperature of 80-100 ℃, and the solution is stirred and heated for 5-10 min;
(3) Adding ascorbic acid into the heated solution until the solution is brown;
(4) Preserving the heat of the brown solution in an oil bath for 10-30 min, and then taking out and naturally cooling;
(5) Adding CuCl 2 Adding the solution to the above cooled solution, cuCl 2 And H 2 PdCl 4 At a molar ratio of 10: 1, thenAdding NaOH solution and NH in turn 2 Shaking the OH & HCl solution evenly, and standing at room temperature until the color of the solution becomes brownish green;
(6) Centrifuging the brown green solution, collecting precipitate, centrifuging the precipitate with formaldehyde, washing for several times, and drying to obtain the Pd-Cu with yolk structure 2 And (3) an O catalyst.
The invention firstly utilizes CTAB and H 2 PdCl 4 Reacting with KI in water solution, adding ascorbic acid to prepare mixed solution containing Pd metal particles, and adding CuCl into the mixed solution containing Pd metal particles 2 With alkali liquor to finally prepare Cu 2 Pd-Cu of Yolk structure (Yolk-Shell) of O-coated Pd metal particles 2 An O catalyst; the prepared Yolk structure (Yolk-Shell) Pd-Cu 2 O catalyst, abbreviated as YS-Pd/Cu for English 2 O, the appearance of the electron microscope image is shown as figure 1, and the yolk structure YS-Pd/Cu 2 O in Cu + Under the action of (2), the surface adsorption of CO is favorably weakened 2 C-O bond in (1) to form CO, which is then further reacted with H 2 Hydrogenation reaction is carried out under the catalytic action of Pd to form methanol.
Preferably, in the step (1), the ratio of the addition amount of the deionized water to the CTAB powder is 1 mL: 4-5 mg.
Further, in the step (2), H 2 PdCl 4 The concentration of the solution is 0.01mmol/L, the concentration of the KI solution is 0.1mmol/L, and CTAB aqueous solution and H 2 PdCl 4 The volume ratio of the solution is 20-30: 1.
Further, in the step (3), the concentration of the ascorbic acid solution is 0.1mmol/L.
More preferably, in the step (5), cuCl 2 The concentration of the solution is 0.1mmol/L, and the solution is diluted by 150 to 200 times before being added; the concentration of NaOH solution is 1mmol/L, NH 2 The concentration of the OH & HCl solution was 1mmol/L.
In particular, the yolk structure Pd-Cu prepared in the step (6) 2 O catalyst, the loading of Pd is 1wt%.
Compared with the prior art, the invention has the following beneficial effects:
1. YS provided by the invention-Pd/Cu 2 The synergistic effect of Pd and 1-valent Cu in the O catalyst is favorable for improving the catalytic activity, and the catalytic activity is improved in Cu + By the action of (2), CO is adsorbed on the surface of the catalyst 2 C-O bond in the alloy is easily weakened by Cu + until the alloy is broken to form CO, and then the CO is further reacted with H 2 Hydrogenation reaction is carried out under the catalytic action of Pd to form methanol.
2. The YS-Pd/Cu provided by the invention 2 O catalyst, using Cu 2 Yolk structure YS-Pd/Cu of O-coated Pd nanoparticles 2 The O catalyst has more stable catalytic performance and longer service life;
3. the YS-Pd/Cu provided by the invention 2 O catalyst, the raw material medicament is safe and easy to obtain, and is used for CO 2 The catalytic hydrogenation for preparing the methanol has the advantages of relatively low cost, convenient process flow, simple operation, energy conservation and contribution to engineering popularization.
Drawings
FIG. 1 shows the yolk structure Pd-Cu prepared by the invention 2 O catalyst transmission electron micrograph;
FIG. 2 shows the yolk structure Pd-Cu prepared by the present invention 2 O catalyst and Pd-Cu of common structure 2 O catalyst to CO 2 A histogram of activity comparison results of catalytic hydrogenation to methanol;
FIG. 3 shows the yolk structure Pd-Cu prepared by the present invention 2 O catalyst and Pd-Cu of common structure 2 O catalyst to CO 2 And comparing the stability of the activity of the methanol prepared by catalytic hydrogenation with the test result by a line chart.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described below with reference to various embodiments and the accompanying drawings, and the implementation manner of the present invention includes, but is not limited to, the following embodiments.
Example 1
The YS-Pd/Cu provided by the invention 2 The preparation method of the O catalyst comprises the following steps:
(1) The glass containing 10mL of deionized water and 45mg of CTAB was sonicated until the CTAB powder was completely dissolved.
(2) To the above solution was added 0.5mL of H 2 PdCl 4 (concentration 0.01 mmol/L) and 0.3mL of KI (concentration 0.1 mmol/L).
(3) The solution is stirred evenly. The vial was then placed in an oil bath at 95 ℃ and heated with gentle stirring for 5min.
(4) After stirring under heating for 5min, 0.08mL of ascorbic acid at a concentration of 0.1mmol/L was added, and the solution turned brown, indicating the reduction of Pd ions to Pd metal particles.
(5) After 20min, the solution was removed from the oil bath and cooled for about 1h, which was designated as the Pd seed solution.
(6) 0.5mL of CuCl with a concentration of 0.1mmol/L 2 Mixed with 94mL of deionized water for dilution and added to 1.2mL of the Pd seed solution. 2.5mL of 1mmol/LNaOH and 2mL of 1mmol/LNH were added in succession 2 OH & HCl, shake well. After standing at room temperature for 2h, the solution changed from brown to brownish green in color.
(7) The solution was centrifuged at 5000rpm for 10min and the product collected. The precipitate was redispersed in methanol and the centrifugal washing was repeated twice. Finally, drying the mixture to obtain the yolk structure YS-Pd/Cu with 1wt% of Pd loading 2 The transmission electron microscope picture of the O catalyst is shown in figure 1.
The obtained YS-Pd/Cu 2 O catalyst and a conventional Pd/Cu catalyst with a Pd loading of 1wt% available on the market 2 O catalyst for CO 2 The catalytic hydrogenation is used for preparing methanol, and the operation steps are as follows:
20mg of the catalyst was charged in a quartz reactor having a straight tube diameter of 1cm, and heated to 280 ℃ to effect a reaction. The reactor inlet gas flow rate was 100mL/min, the gas composition was 20% 2 ，20％CO 2 And 60% Ar. The gas components after the reaction were analyzed at the outlet of the reactor using a mass spectrometer.
As shown in FIG. 2, the yolk structure YS-Pd/Cu was compared 2 O and ordinary 1wt% Pd/CuO vs. CO 2 The effect of catalytic hydrogenation can be seen from figure 2, in the yolk structure YS-Pd/Cu 2 By catalysis of O, CO 2 The conversion rate of (2) is up to 85%, wherein, CH 3 The yield of OH reached 73%. Under the catalysis of common Pd/CuO, CO 2 The conversion of (A) is only 58%, where CH 3 OH yield onlyThe content was found to be 23%. Demonstration of yolk structure YS-Pd/Cu 2 O catalyst to CO 2 The catalytic hydrogenation for preparing methanol has higher catalytic activity and selectivity.
As shown in FIG. 3, the yolk structure YS-Pd/Cu was compared 2 O catalyst and ordinary Pd/Cu 2 The O catalyst was compared for activity stability. Stability test was performed on each catalyst, yolk structure YS-Pd/Cu 2 O catalyst and ordinary Pd/Cu 2 The O catalysts were each tested for 20h activity. As can be seen from figure 3, after 20h activity test, the yolk structure YS-Pd/Cu 2 The activity of the O catalyst is not reduced basically, and CO 2 The conversion rate of the catalyst is kept above 80 percent, and the normal Pd/Cu 2 After 20 hours, the deactivation phenomenon of the catalytic activity of the O catalyst is serious, and the catalytic activity is rapidly reduced after 6 hours of reaction. Cu 2 The yolk structure of the O-coated Pd nano-particles is beneficial to the stability of the Pd particles, so that the catalyst has more stable activity and longer service life.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (3)
1. For CO 2 Pd-Cu for preparing methanol by catalytic hydrogenation 2 The preparation method of the O catalyst is characterized by comprising the following steps:
(1) Completely dissolving CTAB powder in deionized water to obtain a CTAB aqueous solution, wherein the ratio of the addition amount of the deionized water to the addition amount of the CTAB powder is 1mL to 4-5 mg;
(2) Adding H to the above CTAB aqueous solution 2 PdCl 4 Solution and KI solution, the H 2 PdCl 4 The molar ratio of the solution to KI is 1: 5-1: 8, the solution is stirred uniformly and then transferred into an oil bath at the temperature of 80-100 ℃, stirring and heating are carried out for 5-10min 2 PdCl 4 The concentration of the solution is 0.01mmol/L, the concentration of the KI solution is 0.1mmol/L, and CTAB aqueous solution and H 2 PdCl 4 Body of solutionThe product ratio is 20-30: 1;
(3) Adding ascorbic acid into the heated solution until the solution is brown;
(4) Preserving the heat of the brown solution in an oil bath for 10-30 min, and then taking out and naturally cooling;
(5) Adding CuCl 2 Adding the solution to the above cooled solution, cuCl 2 And H 2 PdCl 4 At a molar ratio of 10: 1, and sequentially adding NaOH solution and NH 2 Shaking the OH & HCl solution evenly, and standing at room temperature until the color of the solution becomes brownish green; cuCl 2 The concentration of the solution is 0.1mmol/L, and the solution is diluted by 150 to 200 times before being added; the concentration of NaOH solution is 1mmol/L, NH 2 The concentration of the OH & HCl solution is 1mmol/L;
(6) Centrifuging the brown green solution, collecting precipitate, centrifuging the precipitate with formaldehyde, washing for several times, and drying to obtain the Pd-Cu with yolk structure 2 And (3) an O catalyst.
2. The process according to claim 1, wherein in the step (3), the concentration of the ascorbic acid solution is 0.1mmol/L.
3. The method according to claim 1, wherein the yolk-structured Pd-Cu is obtained in the step (6) 2 O catalyst, the loading of Pd is 1wt%.
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| CN111215147A (en) * | 2020-02-19 | 2020-06-02 | 中国科学技术大学 | Supported yolk-eggshell structure nano catalyst and preparation method thereof |
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| JP5772593B2 (en) * | 2009-05-14 | 2015-09-02 | 宇部興産株式会社 | CuPd alloy nanoparticles, composition and composition for catalyst, and method for producing CuPd alloy nanoparticles |
| CN103977814B (en) * | 2014-05-14 | 2016-06-22 | 中国科学技术大学 | Palladium-cuprous nano Catalysts and its preparation method that size is controlled and catalytic applications |
| KR101688111B1 (en) * | 2015-08-03 | 2016-12-21 | 한국과학기술원 | Zinc based catalyst particle having core-shell structure and methanation of carbon dioxide using the same |
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| 党韶丽 ; 徐凯 ; 宁静慧 ; 潘哲 ; .前驱体(AuCl_3)的量对立方体氧化亚铜-金异质结构材料催化降解性能的影响.2020,(05),全文. * |
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