CN109364979B - MCM-41/Sn-Pd catalyst, preparation method and application - Google Patents
MCM-41/Sn-Pd catalyst, preparation method and application Download PDFInfo
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Abstract
The invention provides an MCM-41/Sn-Pd catalyst, a preparation method and application thereof, wherein a basic molecular sieve MCM-41 doped tin element loaded nano metal particle palladium (MCM-41/Sn-Pd) catalyst is prepared by a chemical reduction method and is used for preparing pyruvic acid by catalytic oxidation of 1, 2-propylene glycol under high pressure. The catalyst has high dosage and activity, and can prepare pyruvic acid with high yield and high selectivity under experimental conditions.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a catalyst, a preparation method and application thereof.
Background
Pyruvic acid belongs to a fine chemical and is applied to the industries of medicines, cosmetics, foods and the like. The pyruvic acid is prepared by distilling a mixture of tartaric acid and potassium bisulfate at 220 ℃ and then vacuum rectifying distillate. Compared with a biological enzyme catalysis method, the method has the characteristic of high generation rate, but has the defects of environmental unfriendliness, high cost and the like. Therefore, the chemical method for preparing pyruvic acid by catalyzing biomass derivatives (such as glycerol and 1, 2-propylene glycol) attracts great attention of researchers. Since 1, 2-propanediol has two adjacent hydroxyl groups, it can be efficiently converted to pyruvate by deep oxidation by employing catalytic oxidation, biofermentation, or electrocatalytic oxidation pathways. Therefore, 1, 2-propanediol is the best raw material for preparing pyruvic acid. Compared with the conversion methods mentioned above, the method for directly catalyzing and oxidizing the 1, 2-propylene glycol by designing a high-efficiency catalyst can convert the 1, 2-propylene glycol into the pyruvic acid in high efficiency and environment-friendliness.
Disclosure of Invention
The invention prepares a basic molecular sieve MCM-41 doped tin element load nano metal particle palladium (MCM-41/Sn-Pd) catalyst by a chemical reduction method, and is used for preparing pyruvic acid by catalytic oxidation of 1, 2-propylene glycol under high pressure. The catalyst has high dosage and activity, and can prepare pyruvic acid with high yield and high selectivity under experimental conditions.
The technical scheme of the invention is as follows:
a method for preparing MCM-41/Sn-Pd catalyst is characterized by comprising the following steps:
step 1, preparing a template agent: weighing a template agent and a surfactant at normal temperature, dissolving the template agent and the surfactant into deionized water, and dropwise adding ammonia water during vigorous stirring to prepare the template agent;
step 2, preparing MCM-41/Sn: reacting tin chloride (SnCl) at normal temperature4·5H2O) is dissolved into tetraethyl orthosilicate (TEOS) to form white colloid; continuously and violently stirring the white colloid for 1 hour, transferring the white colloid into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, and repeatedly washing the white colloid for many times by using deionized water and absolute ethyl alcohol after crystallization to obtain white molecular sieve raw powder;
step 3, removing the template: fully grinding the dried molecular sieve raw powder into powder, and then putting the powder into a quartz tube furnace for roasting to obtain MCM-41/Sn mesoporous molecular sieve powder without the template;
step 4, preparing a catalyst MCM-41/Sn-Pd: weighing MCM-41/Sn mesoporous molecular sieve powder, adding the powder into deionized water, and violently stirring until the powder is completely dissolved; then PdCl is added dropwise2-a HCl solution; and (3) after fully stirring, adding a reducing agent to reduce metal Pd, then washing the precipitate for multiple times by using deionized water and absolute ethyl alcohol, and finally drying in vacuum to obtain the MCM-41/Sn-Pd nano catalyst.
Further, in the step 2, the molar ratio of the silicon element to the tin element in the mixed solution of tin chloride and tetraethyl orthosilicate is maintained at 8 to 30.
Further, in the step 4, the loading amounts of the nano metal particles Pd are respectively 1% -4%.
Further, the template and surfactant are cetyltrimethylammonium bromide (CTAB).
Further, the reducing agent is ascorbic acid.
The MCM-41/Sn-Pd catalyst prepared by the preparation method is characterized in that the catalyst is spherical, a tin element doped in the alkaline molecular sieve MCM-41 is positioned in a framework of the catalyst, and nano metal particle palladium is loaded on the surface of the alkaline molecular sieve MCM-41.
The method for preparing pyruvic acid by catalyzing 1, 2-propanediol under high pressure by using the MCM-41/Sn-Pd catalyst is characterized by comprising the following steps of:
firstly, sequentially adding 1, 2-propylene glycol, deionized water and an MCM-41/Sn-Pd catalyst into a beaker to form a raw material, and adjusting the pH of the raw material to be alkalescent by using a NaOH solution after the raw material is completely dissolved; then the reactant is poured into a quick-opening reaction kettle for reaction.
Au, Pd, Pt single metal or double metal supported catalysts show high catalytic activity in the reaction of catalytic oxidation of 1, 2-propylene glycol under alkaline conditions. The promoters of Sn, Bi, Te and the like have a geometric (blocking) effect on an active site taking noble metal as a center, thereby providing different coordination environments for a substrate and further improving the catalytic performance of the original catalyst. Moreover, the higher affinity of the promoters to oxygen can protect the active component Pt or Pd of the catalyst from excessive oxidation, so that the substrate 1, 2-propylene glycol can be oxidized more deeply. Meanwhile, the carrier is prepared by doping the promoter Sn in situ in the porous alkaline molecular sieve, so that the loss of the promoter and active metal can be reduced, the catalytic efficiency and the service life of the catalyst are improved, the physical and chemical stability and the environment-friendly performance of the catalyst are further improved, and the catalyst capable of catalyzing 1, 2-propylene glycol well is prepared.
The invention prepares an alkaline molecular sieve MCM-41 doped cocatalyst tin element and a supported nano metal particle palladium (MCM-41/Sn-Pd) catalyst by a chemical reduction method, and is used for the reaction of preparing pyruvic acid by catalytically oxidizing 1, 2-propylene glycol under high pressure. And comparing the catalytic effect of different Si/Sn catalysts. The catalyst has high activity, and can prepare pyruvic acid with high yield and high selectivity under experimental conditions.
Drawings
FIG. 1 shows MCM-41/Sn-Pd obtained by the preparation method described in example 1 (Si/Sn ═ 15)5X-ray diffraction pattern of (a).
FIG. 2 shows MCM-41/Sn-Pd obtained by the preparation method described in example 1 (Si/Sn ═ 15)5Scanning electron microscopy of (a).
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1
(1) Preparing a template agent: weighing 2.77g of hexadecyl trimethyl ammonium bromide (CTAB) as a template agent and a surfactant at normal temperature, dissolving 120g of deionized water, and dropwise adding 10.5ml of ammonia water during vigorous stirring to prepare the template agent.
(2) Preparing MCM-41/Sn: 1.17g of crystalline tin chloride (SnCl) are weighed out at room temperature4·5H2O) was dissolved in 11.2ml of tetraethyl orthosilicate (TEOS) so that the molar ratio of elemental silicon to elemental tin in the mixed solution was 15. The template agent was vigorously stirred for 10 minutes, and then the mixed solution was slowly dropped into the template for 15 minutes. And (3) continuously and violently stirring the white colloid for 1 hour, transferring the white colloid into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, and crystallizing the white colloid in a drying oven at the temperature of 110 ℃ for 48 hours. Then repeatedly washing the molecular sieve by using deionized water and absolute ethyl alcohol for many times, and drying the molecular sieve at 60 ℃ for 16 hours to obtain white molecular sieve raw powder.
(3) Removing the template: and fully grinding the dried molecular sieve raw powder into powder, and then putting the powder into a quartz tube furnace for roasting. The roasting procedure is as follows: the room temperature is raised to 200 ℃ by 5 ℃/min and is kept for 2h, and then the room temperature is raised to 55 ℃ by 2 ℃/min and is kept for 6 h. Obtaining MCM-41/Sn mesoporous molecular sieve powder without the template.
(4) Preparation of catalyst MCM-41/Sn-Pd: accurately weighing 0.5g MCM-41/Sn mesoporous molecular sieve powder, adding the powder into 50ml deionized water, and violently stirring to completely dissolve the molecular sieve. Then 5ml of a 0.02mol/L solution of PdCl2-HCl are added dropwise. Stirring thoroughly for 1h, adding 0.05g ascorbic acid to reduce metal Pd, stirring for 0.5h, washing with deionized water and anhydrous ethanol for multiple times, and vacuum drying at 90 deg.C for 12h to obtain MCM-41/Sn-Pd with Si/Sn ═ 155And (3) a nano catalyst.
In the technical schemeTetraethyl orthosilicate, SnCl4·5H2O，PdCl2HCl, the function of which is to provide Si, respectively4+，Sn4+And Pd2+。
FIG. 1 and FIG. 2 are an X-ray diffraction diagram and a scanning electron microscope diagram of the catalyst, respectively, and it can be seen from FIG. 1 that metallic palladium is well supported on a catalyst carrier, and no characteristic peak of Sn element appears in the test result because Sn element is well doped into the catalyst carrier skeleton, which is beneficial to protecting the promoter Sn element from loss. It can be seen from fig. 2 that the morphology of the catalyst is uniform and spherical, and the structure has a higher specific surface area to provide more reactive sites for the reaction, which is beneficial to improving the activity of the catalyst.
(5) Catalytic 1, 2-propanediol: first, 0.04 Mmol/L1, 2-propanediol, 3mg/mL catalyst, 40mL water, and a solution having a concentration of 50mL were sequentially added to a 50mL beaker to form a mixed solution, and the pH of the mixed solution was adjusted to 8 with a solution of 0.1M NaOH. The reaction was then poured into a 250ml quick-open autoclave. Then the reaction kettle is installed, the vent valve is kept open, oxygen is slowly introduced, and the gas in the reaction kettle is replaced by the oxygen. And after 5 minutes, closing the air outlet valve, and closing the air inlet valve when the air pressure in the reaction kettle meets the experimental requirements and checking the air tightness of the reaction kettle. And after the air tightness of the reaction kettle is determined to be good, installing a heating sleeve on the reaction kettle, setting the heating temperature to be 80 ℃ and the rotating speed of a stirrer to be 600r/min, starting the stirrer to start timing reaction for 8 hours when the temperature of condensed water reaches 80 ℃. After the reaction is finished, the condensed water in the reaction kettle is started, the pressure in the kettle is reduced to zero through the exhaust valve after the temperature is reduced to the room temperature, and the reaction kettle is started to take 5ml of sample.
After the reaction was completed, the conversion of 1, 2-propanediol was measured by gas chromatography using an internal standard method, the internal standard being n-butanol. And analyzing and calculating the selectivity of pyruvic acid in the reaction product by adopting high performance liquid chromatography.
Example 2
Like example 1, only the 1, 2-propanediol solution in step (5) of example 1 was changed to 0.02Mmol/L and 0.08Mmol/L, respectively. The results are shown in Table 1. The results show that the conversion rate of the 1, 2-propanediol is increased and the selectivity of the pyruvic acid is slightly improved along with the increase of the concentration of the 1, 2-propanediol, and the catalyst has higher activity and keeps higher conversion rate and selectivity to the 1, 2-propanediol and the pyruvic acid within a certain substrate concentration range under experimental conditions.
TABLE 1 Effect of different 1, 2-propanediol concentrations on the conversion of the final feedstock and the selectivity of the reaction products
| 1, 2-propanediol concentration (Mmol/L) | Conversion of 1, 2-propanediol (%) | Pyruvic acid selectivity (%) |
| 0.02 | 87 | 65.1 |
| 0.04 | 90 | 76.5 |
| 0.08 | 94 | 80.5 |
Example 3
The same as example 1, except that the temperatures of the reactions in the step (5) of example 1 were changed to 100 ℃ and 120 ℃, respectively, and then the catalyzed 1, 2-propanediol reaction was carried out, the results were shown in Table 2. The result shows that the conversion rate of the 1, 2-propylene glycol and the selectivity of the pyruvic acid are improved along with the increase of the reaction temperature, which indicates that the catalyst has higher activity and keeps higher conversion rate and selectivity to the 1, 2-propylene glycol and the pyruvic acid within a certain reaction temperature range under experimental conditions.
TABLE 2 Effect of different reaction temperatures on the conversion of the final starting materials and the selectivity of the reaction products
| Reaction temperature (. degree.C.) | Conversion of 1, 2-propanediol (%) | Pyruvic acid selectivity (%) |
| 80 | 78 | 72.1 |
| 100 | 90 | 76.5 |
| 120 | 92 | 80 |
Example 4
As in example 1, the Si/Sn ratio of the catalyst used in step (2) of example 1 was changed to 8, 30. The specific raw material addition amount in the catalyst preparation process is as follows: 0.6g of crystalline tin chloride (SnCl) is weighed out at room temperature when the Si/Sn ratio is 84·5H2O) was dissolved in 11.2ml of tetraethyl orthosilicate (TEOS) so that the molar ratio of elemental silicon to elemental tin in the mixed solution was 8. 0.6g of crystalline tin chloride (SnCl) was added when the Si/Sn ratio was 304·5H2O) preparation step of mixing with 11.2ml of tetraethyl orthosilicate (TEOS) at normal temperature and the rest of the catalystThe procedure was the same as in the case of Si/Sn of 15. The final results are shown in Table 3. As a result, the conversion rate of the 1, 2-propylene glycol is reduced and the selectivity of the pyruvic acid is reduced along with the increase of the ratio of the silicon element to the tin element, and the experiments show that the catalyst maintains higher activity in a certain range of silicon-tin ratio, and the optimal ratio of the silicon to the tin in the current experimental result is 8.
TABLE 3 Effect of different oxygen pressures on the conversion of the final feedstock and the selectivity of the reaction products
| Si/Sn | Conversion of 1, 2-propanediol (%) | Pyruvic acid selectivity (%) |
| 8 | 92 | 80.1 |
| 15 | 90 | 76.5 |
| 30 | 88 | 62.1 |
Example 5
As in example 1, only the catalyst concentration in step (5) of example 1 was changed to 1.5mg/mL or 6 mg/mL. The results are shown in Table 4. The results show that the conversion rate of the 1, 2-propylene glycol is increased and the selectivity of the pyruvic acid is slightly improved along with the increase of the used catalyst, which indicates that the catalyst has higher activity and keeps higher conversion rate and selectivity to the 1, 2-propylene glycol and the pyruvic acid within a certain catalyst concentration range under experimental conditions.
TABLE 4 Effect of different catalyst concentrations on the conversion of the final feedstock and the selectivity of the reaction products
| Catalyst concentration (mg/mL) | Conversion of 1, 2-propanediol (%) | Pyruvic acid selectivity (%) |
| 1.5 | 88 | 72.1 |
| 3 | 90 | 76.5 |
| 6 | 92 | 81.2 |
Example 6
The reaction time in step (5) of example 1 was changed to 4 hours and 12 hours, respectively, as in example 1. The catalytic reaction was then carried out, the final results of which are shown in Table 5. The result shows that the conversion rate of the 1, 2-propylene glycol is increased and the selectivity of the pyruvic acid is slightly increased along with the prolonging of the catalytic reaction time, which shows that the catalyst has higher activity and keeps higher conversion rate and selectivity to the 1, 2-propylene glycol and the pyruvic acid within a certain reaction time range under experimental conditions.
TABLE 5 Effect of different reaction times on the conversion of the final starting materials and the selectivity of the reaction products
| Reaction time (h) | Conversion of 1, 2-propanediol (%) | Pyruvic acid selectivity (%) |
| 4 | 88 | 62.1 |
| 8 | 90 | 76.5 |
| 12 | 92.2 | 78.6 |
Example 7
As in example 1, the reaction pressure in step (5) of example 1 was changed to 0.5MPa or 2 MPa. The catalytic reaction was then carried out, the final results of which are shown in Table 6. The result shows that the conversion rate of the 1, 2-propylene glycol is increased and the selectivity of the pyruvic acid is slightly increased along with the prolonging of the catalytic reaction time, which shows that the catalyst has higher activity and keeps higher conversion rate and selectivity to the 1, 2-propylene glycol and the pyruvic acid within a certain reaction pressure range under experimental conditions.
| Reaction pressure (MPa) | Conversion of 1, 2-propanediol (%) | Pyruvic acid selectivity (%) |
| 0.5 | 83 | 65.1 |
| 1 | 90 | 76.5 |
| 2 | 93.2 | 80.6 |
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (7)
1. A method for preparing MCM-41/Sn-Pd catalyst is characterized by comprising the following steps:
step 1, preparing a template agent: weighing a template agent and a surfactant at normal temperature, dissolving the template agent and the surfactant into deionized water, and dropwise adding ammonia water during vigorous stirring to prepare the template agent;
step 2, preparing MCM-41/Sn: dissolving tin chloride into tetraethyl orthosilicate (TEOS) at normal temperature to form white colloid; wherein, the molar ratio of silicon element to tin element in the mixed solution of tin chloride and tetraethyl orthosilicate is kept between 8 and 30; continuously and violently stirring the white colloid for 1 hour, transferring the white colloid into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, and repeatedly washing the white colloid for many times by using deionized water and absolute ethyl alcohol after crystallization to obtain white molecular sieve raw powder;
step 3, removing the template: fully grinding the dried molecular sieve raw powder into powder, and then putting the powder into a quartz tube furnace for roasting to obtain MCM-41/Sn mesoporous molecular sieve powder without the template;
step 4, preparing a catalyst MCM-41/Sn-Pd: weighing MCM-41/Sn mesoporous molecular sieve powder, adding the powder into deionized water, and violently stirring until the powder is completely dissolved; then PdCl is added dropwise2-a HCl solution; after fully stirring, adding a reducing agent to reduce metal Pd, so that the loading capacity of the nano metal particle Pd is 1% -4%; then washing the precipitate for multiple times by using deionized water and absolute ethyl alcohol, and finally drying in vacuum to obtain the MCM-41/Sn-Pd nano catalyst.
2. The method of claim 1, wherein the template and surfactant are cetyltrimethylammonium bromide (CTAB).
3. The method according to claim 1, wherein the reducing agent is ascorbic acid.
4. The MCM-41/Sn-Pd catalyst prepared by the preparation method of claim 1, wherein the catalyst is spherical, the tin element doped in the alkaline molecular sieve MCM-41 is positioned in the framework of the catalyst, and the nano metal particle palladium is loaded on the surface of the alkaline molecular sieve MCM-41.
5. The use of the MCM-41/Sn-Pd catalyst of claim 4 for the preparation of pyruvic acid by catalysis of 1, 2-propanediol at high pressure, characterized by the following steps:
firstly, sequentially adding 1, 2-propylene glycol, deionized water and an MCM-41/Sn-Pd catalyst into a beaker to form a raw material, and adjusting the pH of the raw material to be alkalescent by using a NaOH solution after the raw material is completely dissolved; then the reactant is poured into a quick-opening reaction kettle for reaction.
6. The use of an MCM-41/Sn-Pd catalyst according to claim 5 for the preparation of pyruvic acid at high pressure catalysing 1, 2-propanediol, characterised in that the concentration of 1, 2-propanediol is 0.02-0.08 mmols/L.
7. The use of the MCM-41/Sn-Pd catalyst of claim 5 for the preparation of pyruvic acid under high pressure catalysis of 1, 2-propanediol, characterized in that the concentration of the catalyst is 1.5-6 mg/mL.
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Citations (2)
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| EP0337246A1 (en) * | 1988-04-04 | 1989-10-18 | Research Association For Utilization Of Light Oil | Process for preparing pyruvate |
| CN104193615A (en) * | 2014-05-16 | 2014-12-10 | 江苏大学 | Catalytic oxidation method for 1,2-propanediol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0337246A1 (en) * | 1988-04-04 | 1989-10-18 | Research Association For Utilization Of Light Oil | Process for preparing pyruvate |
| CN104193615A (en) * | 2014-05-16 | 2014-12-10 | 江苏大学 | Catalytic oxidation method for 1,2-propanediol |
Non-Patent Citations (2)
| Title |
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| 1,2-丙二醇合成丙酮酸及丙酮酸甲醋;金宏轩 等;《化学反应工程与工艺》;20080430;第24卷(第2期);第163-167页 * |
| Synthesis, Characterization, and Catalytic Properties of Mesoporous Tin-Containing Analogs of MCM-41;K. Chaudhari et al.;《Journal of Catalysis》;19991231;第183卷;第281-291页 * |
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