CN113941347B - Application of high-efficiency and high-stability nano catalyst with film coating layer - Google Patents

Application of high-efficiency and high-stability nano catalyst with film coating layer Download PDF

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CN113941347B
CN113941347B CN202111112153.1A CN202111112153A CN113941347B CN 113941347 B CN113941347 B CN 113941347B CN 202111112153 A CN202111112153 A CN 202111112153A CN 113941347 B CN113941347 B CN 113941347B
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CN113941347A (en
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张颖
曾翔
陈泽民
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University of Science and Technology of China USTC
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Abstract

The invention discloses application of phosphate substances with a membrane coating structure in preparation of succinic acid by maleic anhydride hydrogenation, preparation of gamma-valerolactone by levulinic acid hydrogenation, preparation of benzyl alcohol by benzaldehyde hydrogenation and preparation of sorbitol by glucose hydrogenation. The method can form the metal phosphide active site which has excellent hydrogenation activity and can be stably exposed in the air without inactivation, and the method can form a film coating structure on the surface of the active site, thereby preventing the active site from inactivation in an acid environment and avoiding the problem of catalyst loss. The preparation method is simple in preparation process, the prepared catalyst is good in recycling performance, reaction products are easy to separate from the catalyst and a solvent system, the reaction period is short, and the method is suitable for industrial production and has a very wide application prospect.

Description

Application of high-efficiency and high-stability nano catalyst with film coating layer
Technical Field
The invention relates to the technical field of catalytic hydrogenation, in particular to an application of a high-efficiency and high-stability nano catalyst with a film coating layer. In particular to application of a catalyst in preparation of succinic acid by selective hydrogenation of maleic anhydride, preparation of gamma-valerolactone by selective hydrogenation of levulinic acid, preparation of benzyl alcohol by selective hydrogenation of benzaldehyde and preparation of sorbitol by selective hydrogenation of glucose.
Background
At present, in the industrial conversion process of important bulk platform molecules (such as maleic anhydride, levulinic acid, benzaldehyde, glucose and the like), whether the catalyst has oxidation resistance and acid corrosion resistance so as to efficiently and stably perform the catalytic action is an important index for evaluating whether the catalyst can promote the platform molecules to perform industrial upgrading conversion.
The catalytic reaction environment becomes acidic after the levulinic acid and the succinic acid, which is a hydrogenation product of maleic anhydride, are dissolved in water. This puts severe demands on the acid corrosion resistance and high stability of the catalyst. Among the non-noble metal catalysts, Raney Ni, Ni/CeO2, Ni/diatomite, etc. are mainly used, but these catalysts have serious loss phenomenon during the reaction process and the required reaction conditions are very high. The noble metal type catalysts mainly comprise Pd/Al2O3, Ru/AC, Pd/HAP, Pd/C, Pt/C and the like, but the catalytic reaction conditions of the catalysts are severe, and the catalysts have the problem of inactivation in an acidic environment.
The traditional catalyst for preparing benzyl alcohol from benzaldehyde and sorbitol from glucose mainly comprises a Cu-Cr catalyst and Raney Ni. However, the metal loss and serious chromium pollution of the traditional catalyst are serious, and benzaldehyde and glucose are easy to coke at higher temperature and under the condition of acid catalysis in the traditional preparation method, so that the conversion efficiency of benzaldehyde and glucose is low, and the yield of corresponding benzyl alcohol and sorbitol is also low.
In addition, in industrial catalysis, strict requirements are also put on the oxidation resistance of the catalyst, because the hydrogenation catalyst generally needs to be subjected to a reduction process to have the catalytic hydrogenation function. However, once the reduced catalyst, especially the non-noble metal catalyst, is exposed to air for a long time, the catalyst is gradually deactivated, which affects the practical application of the catalyst.
Therefore, the key technology for preparing succinic acid, gamma-valerolactone, benzyl alcohol and sorbitol by catalyzing maleic anhydride, levulinic acid, benzaldehyde and glucose through selective hydrogenation is to develop a green, efficient, stable, oxidation-resistant and acid corrosion-resistant catalyst.
Disclosure of Invention
In view of the above, the invention provides an application of a high-efficiency and high-stability nano catalyst with a film coating layer in preparation of succinic acid by maleic anhydride hydrogenation, preparation of gamma-valerolactone by levulinic acid hydrogenation, preparation of benzyl alcohol by benzaldehyde hydrogenation, and preparation of sorbitol by glucose hydrogenation. The catalyst with the membrane-coated structure is acid-resistant and oxidation-resistant, the metal loaded on the catalyst is stable and not easy to run off, and the catalyst can catalyze the hydrogenation of the substrate under harsh reaction conditions.
The invention is realized by the following technical scheme: the application of the high-efficiency and high-stability nano catalyst with the film coating layer is applied to preparation of succinic acid by maleic anhydride hydrogenation, preparation of gamma-valerolactone by levulinic acid hydrogenation, preparation of benzyl alcohol by benzaldehyde hydrogenation or preparation of sorbitol by glucose hydrogenation; the catalyst is phosphate B (PO) 4 ) a As a carrier in phosphate B (PO) 4 ) a The carrier is loaded with metal phosphide AP b Particles in metal phosphide AP b The surface of the particles is coated with BO c A film coating layer, wherein A is one or more transition metals in groups VIIIB, IB and IIB of the periodic table, B is one or more transition metals in yttrium (Y), titanium (Ti), manganese (Mn), lanthanum (La), chromium (Cr) and lead (Pb), and a, B and c independently take values under the condition of valence bond balance of a chemical formula; the catalyst is used for catalyzing maleic anhydride hydrogenation to prepare succinic acid, levulinic acid hydrogenation to prepare gamma-valerolactone, benzaldehyde hydrogenation to prepare benzyl alcohol or glucose hydrogenation to prepare sorbitol, and the reaction process comprises the following steps: adding maleic anhydride, levulinic acid, benzaldehyde or glucose and a catalyst into a reaction kettle together, and adding H 2 Washing the reaction kettle, replacing the air in the reaction kettle, and then keeping the reaction kettle in H 2 The pressure is 0.1-5MPa, the reaction is carried out for 2-15h under the condition of 0-180 ℃, and then the mixture is cooled and decompressed.
As a further improvement to the above, a is one or more of palladium (Pd), iridium (Ir), platinum (Pt), nickel (Ni), copper (Cu), and cobalt (Co).
As a further improvement to the above scheme, the concentration of the maleic anhydride, levulinic acid, benzaldehyde and glucose in the catalytic reaction is 0.5 to 1 wt%.
As a further improvement to the above, the amount of the supported metal element B in the catalyst in the catalytic reaction is 1 to 15% by weight.
As a further improvement of the scheme, the reaction temperature in the reaction of preparing succinic acid by maleic anhydride hydrogenation is 30-150 ℃, the reaction temperature in the reaction of preparing gamma-valerolactone by levulinic acid hydrogenation is 30-160 ℃, the reaction temperature in the reaction of preparing benzyl alcohol by benzaldehyde hydrogenation is 30-140 ℃, and the reaction temperature in the reaction of preparing sorbitol by glucose hydrogenation is 0-180 ℃.
As a further improvement to the above scheme, the catalyst is prepared by the following method:
step one, preparing a pre-salt carrier, namely sequentially and uniformly mixing soluble salt of B, citric acid, urea and diammonium hydrogen phosphate, and drying and calcining after hydrothermal treatment to obtain the pre-salt carrier;
secondly, loading, namely dissolving nitrate or acetate of the carrier A in acetone to prepare an acetone solution of the carrier A, and soaking the pre-salt carrier prepared in the first step in the acetone solution of the carrier A;
and step three, drying, calcining and reducing, namely taking out the pre-salt carrier treated in the step two, drying, calcining, and reducing in a hydrogen atmosphere to obtain the high-efficiency and high-stability nano catalyst with the film coating layer.
As a further improvement to the scheme, the concentration of the acetone solution of the A is 3-12 mmol/L; the dipping time in the second step is 12-24 hours; in the third step, the drying temperature is 20-120 ℃, the drying time is 6-12 hours, the calcining temperature is 600 ℃, the calcining time is 2 hours, the reducing temperature is 600-.
As a further improvement to the above scheme, the preparation method of the pre-salt carrier in the first step comprises the following specific steps: adding soluble salt B into a hydrothermal kettle, adding water, stirring to dissolve the soluble salt B, sequentially adding citric acid, urea and diammonium hydrogen phosphate under a stirring state, transferring the hydrothermal kettle into an oven to perform hydrothermal reaction after stirring is finished, and filtering, drying and calcining after the hydrothermal reaction is finished to obtain a salt carrier; the molar ratio of the soluble salt of B, citric acid, urea and diammonium hydrogen phosphate is 1: 3: 6: 1 to 5.
As a further improvement of the above scheme, in the specific method for preparing the salt carrier in the first step, each substance is sequentially added with stirring at an interval of 15 minutes, diammonium hydrogen phosphate is added, stirring is continued for 15 minutes, and then the mixture is transferred into an oven for hydrothermal reaction at 160 ℃ for 13 hours, drying temperature is 105 ℃, calcining temperature is 550 ℃ and calcining time is 2 hours.
Compared with the prior art, the invention has the following advantages: the invention adopts a scheme of calcining after loading and then reducing to prepare the catalyst, so that the loaded metal A is converted into AP b The metal-carbon double bond activation catalyst is converted and coated on the surface of a salt carrier to form a film coating structure, so that strong metal-carrier strong interaction is formed, a carbon-carbon double bond and a carbon-oxygen double bond can be well activated, metal is prevented from being inactivated in an acidic environment in which an acidic product exists, and meanwhile, the coating layer can prevent the reacted acidic product from contacting with the salt carrier, so that the problem of catalyst loss can be effectively avoided.
Because the salt carrier presents weak acidity, the adsorption and activation of the substrate in the reaction process can be obviously promoted; the salt carrier has strong metal ion adsorption capacity, can ensure that the dispersion effect of the loaded metal is very good and the loaded metal shows higher catalytic activity, ensures that the catalytic reaction can be carried out under the condition of mild temperature, and has quite high conversion rate and high selectivity, and experiments show that the conversion rate of maleic anhydride and the yield of succinic acid can both reach 100 percent under the mild condition.
Drawings
FIG. 1 is an SEM photograph of a manganese pyrophosphate pre-salt support of example 1;
FIG. 2 shows Co/Mn in example 1 3 (PO 4 ) 2 SEM photograph of (a).
FIG. 3 shows Co/Mn in example 1 3 (PO 4 ) 2 XRD pattern of (a).
FIG. 4 shows Co/Mn in example 1 3 (PO 4 ) 2 HRTEM of the upper film clad structure.
FIG. 5 shows Co/Mn in example 1 3 (PO 4 ) 2 Maps photos.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples. In the following examples, unless otherwise specified, all methods used are conventional and all reagents used are commercially available.
Example 1
Preparation of high-efficiency and high-stability nano catalyst with film coating layer
Step one, preparing a pre-salt carrier.
1964mg of tetrahydrate manganese acetate, 5043mg of citric acid, 2882mg of urea and 3169.4mg of diammonium hydrogen phosphate are sequentially added into a 100mL hydrothermal kettle, the stirring interval time of each substance is 15 minutes, then the hydrothermal kettle is moved into an oven for hydrothermal reaction at 160 ℃ for 13 hours, and after the hydrothermal kettle is completely cooled, the hydrothermal kettle is filtered and washed, dried at 105 ℃ and calcined at 550 ℃ for 2 hours to obtain the manganese pyrophosphate pre-salt carrier.
And step two, loading.
Adopts a catalyst containing 871.5mg Co (NO) 3 ) 2 100mL of acetone solution (2), 1.00g of manganese pyrophosphate pre-salt carrier is immersed, and the solution is stirred for 24 hours until the adsorption equilibrium is reached.
And step three, drying, calcining and reducing.
Filtering the adsorbed pre-salt carrier, washing with acetone, drying at 105 deg.C for 10h, calcining at 600 deg.C in air for 2h, and reducing with hydrogen at 800 deg.C for 3h to obtain Co catalyst with 15% of supported cobalt mass fraction, abbreviated as Co/Mn 3 (PO 4 ) 2 。
The structure of the catalyst can be known through characterization analysis as follows: manganese phosphate is taken as a carrier, and metal phosphide C is loaded on the manganese phosphate carriero 2 P particles in metal phosphide Co 2 The surface of the P particle is coated with MnO x And (5) coating the layer by a film.
FIG. 1 is an SEM photograph of manganese phosphate pre-salt carrier, FIG. 2 is an SEM photograph of Co/MnP-3, in which the round particles are Co 2 P particles. Comparing fig. 1 and fig. 2, it is found that the morphology is more compact after manganese pyrophosphate is calcined and reduced to manganese phosphate, after Co is loaded on the carrier, a similar ball is formed and attached on the surface of the carrier, and Co species are uniformly dispersed on the carrier, which indicates that the cobalt species has good dispersibility. The average particle size of the cobalt species was calculated to be only 61.9nm, and the cobalt species were very uniformly dispersed on the support MnP-3. As can be seen from the X-ray diffraction analysis of the product, Co is observed on the XRD spectrogram (figure 3) after the metal is loaded 2 Appearance of P diffraction Peak, which indicates Co 2 The appearance of P species on the support, indicating that the Co species is Co 2 The form of P is supported on a carrier. Fig. 4 is an HRTEM photograph of the edge of a spherical particle in the catalyst, which shows that the surface of the Co particle is coated with a film. The Co/Mn ratio of the catalyst can be clearly seen from the EDS elemental map (FIG. 5) 3 (PO 4 ) 2 The element distribution of (1) and the combination of XRD and HRTEM can obtain Co 2 P is MnO x Conclusion that the film of the structure is tightly wrapped.
It is believed that the hydrogen reduction conditions of the manganese pyrophosphate pre-salt support combined with metallic Co significantly promote the conversion of metallic Co to Co 2 P species are converted, and a coating film structure is formed on the surface of the salt carrier, so that strong metal-carrier strong interaction is formed, metal agglomeration and leaching can be prevented, and the catalyst can show better catalytic activity and stability.
Respectively loading metal Pd, Ir, Pt, Ru, Rh, Ag, Au, Ni, Cu, Co and Fe to YPO 4 、Ti 3 (PO 4 ) 4 、AlPO 4 、CrPO 4 、Pb(PO 4 ) 2 And (4) obtaining the supported molding agents of different carriers on the carrier. Co is selected from the raw materials, and supported catalysts of different carriers, namely Co/YPO, are prepared 4 、Co/Ti 3 (PO 4 ) 4 、Co/AlPO 4 、Co/CrPO 4 、Co/LaPO 4 The preparation method is the same as Co/MnP-3. The YPO was found after HRTEM characterization of each of them 4 、Ti 3 (PO 4 ) 4 、AlPO 4 、CrPO 4 、LaPO 4 The phenomenon of a film-coated structure also occurs on the carrier.
Non-noble metal Ni is also selected to prepare supported catalysts Ni/MnP-3 and Ni/Ti with different carriers 3 (PO 4 ) 4 、Ni/LaPO 4 Noble metals Pd and Ru are selected to prepare load type catalysts Pd/MnP-3 and Ru/MnP-3 of different carriers. The phenomenon of a film coating structure is also found when Ni, Pd and Ru are loaded.
The membrane coating structure forms strong metal-carrier interaction on the surface of the catalyst, can generate good activation effect on carbon-carbon double bonds and carbon-oxygen double bonds and prevent metal from being inactivated in an acid environment in which an acid product exists, and simultaneously can prevent the acid product of the reaction from contacting with a salt carrier, so that the problem of catalyst loss can be effectively avoided; the salt carrier has weak acidity and strong metal ion adsorption capacity, can obviously promote the adsorption and activation of substrates in the reaction process, can show higher catalytic activity due to good dispersion of the supported metal, enables the catalytic reaction to be carried out under the condition of mild temperature, and has quite high conversion rate and high selectivity.
Example 2
A method for preparing succinic acid by catalyzing maleic anhydride hydrogenation, preparing gamma-valerolactone by hydrogenating levulinic acid, preparing benzyl alcohol by hydrogenating benzaldehyde or preparing sorbitol by hydrogenating glucose by using the catalyst prepared in example 1. The catalytic reaction process is as follows: adding reaction substrates and a catalyst into a 25mL reaction kettle, adding purified water to adjust the concentration of the reaction substrates to be 0.5-1 wt% (mass fraction), and firstly filling H into the reaction kettle 2 Then discharging (repeating at least 5 times) to remove air, and finally charging H 2 Reacting under 0.1-5Mpa and 0-180 deg.C. After the reaction for a predetermined time, the reaction mixture was cooled, degassed, filtered to separate the catalyst from the reaction mixture, diluted with ethanol, and analyzed by gas chromatography.
The gas chromatography conditions were as follows: GC1690 gas chromatography FID detector, capillary chromatography column (Innovax, 30 m.times.0.250 mm. times.0.25 μm), programmed to start at 40 deg.C and increase to 250 deg.C at a rate of 10 deg.C/min for 10 min. The carrier gas was 99.99% high purity N2 at a flow rate of 1 mL/min.
Examples 3 to 12
Co/Mn as in example 1 3 (PO 4 ) 2 Preparation method of Ni/YPO with different metal loading 4 、Cu/Ti 3 (PO 4 ) 4 、Co/LaPO 4 、Co/CrPO 4 、Pd/Mn 3 (PO 4 ) 2 、Ir/YPO 4 、Pt/Ti 3 (PO 4 ) 4 、Pd/LaPO 4 And Pd/CrPO 4 . The reaction procedure and process operation of example 2 were followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 1, the substrate concentration was 1 wt%, the hydrogen pressure was maintained at 0.1MPa, and the conversion of the reactant and the yield of the product were calculated after the completion of the reaction, and the results are reported in Table 1.
TABLE 1, EXAMPLES 3-12 reaction conditions and test results
Figure GDA0003389845270000061
Figure GDA0003389845270000071
Comparative examples 1 to 12
Co and Pd were loaded on MgO and CeO, respectively, according to the procedures of loading, drying, calcining and reducing in example 1 2 、ZrO 2 、TiO 2 、Al 2 O 3 、SiO 2 And (4) obtaining the supported catalysts with different carriers on the carrier.
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 2, the concentration of the substrate was 1 wt%, the hydrogen pressure was maintained at 0.1MPa, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed. The results are reported in Table 2.
TABLE 2 conditions and results for preparing succinic acid in comparative examples 1 to 12
Figure GDA0003389845270000072
The comparison shows that the catalyst provided by the invention has much better effect than the traditional catalyst under the same conditions.
Examples 13 to 22
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 3, the concentration of the substrate was 1 wt%, the hydrogen pressure was maintained at 0.1MPa, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed. The results are reported in Table 3.
TABLE 3 conditions and results for preparation of succinic acid in examples 13 to 22
Figure GDA0003389845270000081
Examples 23 to 32
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 4, the concentration of the substrate in the reaction was 1 wt%, the hydrogen pressure was maintained at 3MPa, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results are reported in Table 4.
Table 4 conditions and results for preparation of succinic acid in examples 23 to 32
Figure GDA0003389845270000082
Figure GDA0003389845270000091
Examples 33 to 42
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 5, the concentration of the substrate in the reaction was 1 wt%, the hydrogen pressure was maintained at 3MPa, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results are reported in Table 5.
TABLE 5 conditions and results for preparation of succinic acid in examples 33-42
Figure GDA0003389845270000092
Examples 43 to 52
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 6, the concentration of the substrate in the reaction was 1 wt%, the hydrogen pressure was maintained at 3MPa, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results are reported in Table 6.
Table 6, conditions and results for preparation of succinic acid in examples 43 to 52
Figure GDA0003389845270000101
Examples 53 to 62
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 7, the concentration of the substrate in the reaction was 1 wt%, the hydrogen pressure was maintained at 3MPa, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results are reported in Table 7.
TABLE 7 conditions and results for preparation of succinic acid in examples 53-62
Figure GDA0003389845270000102
Figure GDA0003389845270000111
Examples 73 to 82
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 8, the concentration of the substrate in the reaction was 1 wt%, the hydrogen pressure was maintained at 3MPa, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results are reported in Table 8.
TABLE 8 conditions and results for preparation of succinic acid in examples 71-80
Figure GDA0003389845270000112
From examples 3-82, Co/Mn is the most preferred hydrogenation performance among the non-noble metal series of catalysts 3 (PO 4 ) 2 The best hydrogenation performance in the noble metal series catalyst is Pd/Mn 3 (PO 4 ) 2 Therefore, Co/Mn is selected in the following examples 3 (PO 4 ) 2 、Pd/Mn 3 (PO 4 ) 2 The two catalysts are used for carrying out catalytic hydrogenation on levulinic acid, benzaldehyde and glucose to prepare corresponding gamma-valerolactone, benzyl alcohol and sorbitol products.
Examples 83 to 92
Co/Mn as in example 1 3 (PO 4 ) 2 Preparation method of catalyst Co/Mn 3 (PO 4 ) 2 、Pd/Mn 3 (PO 4 ) 2 。
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 9, the concentration of the substrate in the reaction was 1 wt%, the hydrogen pressure was maintained at 2MPa, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results are reported in Table 9.
TABLE 9, EXAMPLES 83-92 conditions and results for preparation of gamma-valerolactone
Figure GDA0003389845270000121
Examples 93 to 102
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as shown in Table 10, the substrate concentration was 1 wt%, the hydrogen pressure was adjusted as shown in Table 10, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results are shown in Table 10.
TABLE 10 conditions and results for preparation of gamma-valerolactone in example 103-112
Figure GDA0003389845270000122
Figure GDA0003389845270000131
Example 113-
Co/Mn as in example 1 3 (PO 4 ) 2 Preparation method of catalyst Co/Mn 3 (PO 4 ) 2 、Pd/Mn 3 (PO 4 ) 2 ；
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 11, the concentration of the substrate in the reaction was 1 wt%, the hydrogen pressure was maintained at 2MPa, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results are shown in Table 11.
TABLE 11 conditions and results for the preparation of benzyl alcohol in example 103-112
Figure GDA0003389845270000132
Figure GDA0003389845270000141
Example 113-
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as shown in Table 12, the substrate concentration was 1 wt%, the hydrogen pressure was adjusted as shown in Table 12, and the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results are shown in Table 12.
TABLE 12 conditions and results for the preparation of benzyl alcohol in example 113-122
Figure GDA0003389845270000142
Example 123-
Co/Mn as in example 1 3 (PO 4 ) 2 Preparation method of catalyst Co/Mn 3 (PO 4 ) 2 、Pd/Mn 3 (PO 4 ) 2 ；
The procedure of examples 3 to 12 was followed, and the substrate, catalyst, reaction temperature and reaction time were selected as described in Table 13, the concentration of the substrate in the reaction was 0.5% by weight, the hydrogen pressure was maintained at 2.5MPa, the conversion of the reactant and the yield of the product were calculated after the reaction was completed, and the results of the tests are shown in Table 13.
TABLE 13 conditions and results for the preparation of sorbitol in example 123-
Figure GDA0003389845270000151
Example 135-144
The procedure of the test methods of examples 3 to 12 was carried out, and the substrate, catalyst, reaction time, hydrogen pressure, reaction temperature 120 ℃ and reaction substrate concentration 1 wt% were selected as described in Table 14, and the conversion of the reactant and the yield of the product were calculated after the completion of the reaction, and the results are recorded in Table 14.
TABLE 14 conditions and results for the preparation of sorbitol in example 135-144
Figure GDA0003389845270000152
Figure GDA0003389845270000161
Example 145-
Co/Mn as in example 1 3 (PO 4 ) 2 Preparation method of the catalyst Co/Mn with a film coating structure 3 (PO 4 ) 2 。
Co/Mn of film-free coating structure is prepared simultaneously 3 (PO 4 ) 2 The method comprises the following steps:
step one, preparing a pre-salt carrier.
1964mg of tetrahydrate manganese acetate, 5043mg of citric acid, 2882mg of urea and 3169.4mg of diammonium hydrogen phosphate are sequentially added into a 100mL hydrothermal kettle, the stirring interval time of each substance is 15 minutes, then the hydrothermal kettle is moved into an oven for hydrothermal reaction at 160 ℃ for 13 hours, and after the hydrothermal kettle is completely cooled, the hydrothermal kettle is filtered and washed, dried at 105 ℃ and calcined at 550 ℃ for 2 hours to obtain the manganese pyrophosphate pre-salt carrier.
And step two, loading.
Using a catalyst containing 871.5mg Co (NO) 3 ) 2 The acetone solution (100 mL) is soaked in 1.00g of manganese pyrophosphate pre-salt carrier and stirred for 24h until the adsorption equilibrium is reached.
And step three, drying.
The adsorbed pre-salt support was filtered and washed with acetone and dried at 105 ℃ for 10 h.
Exposing the two catalysts in air for oxidation for 0-4320h for later use.
The results of operating according to the experimental procedures of examples 3 to 12, selecting the substrate, the catalyst, the reaction temperature and the hydrogen pressure as shown in Table 15, with the substrate concentration of the reaction being 1 wt%, calculating the conversion of the reactants and the yield of the product after 10 hours of reaction are shown in Table 15.
TABLE 15 example 177-188Co/Mn 3 (PO 4 ) 2 Results of the antioxidant Capacity test
Figure GDA0003389845270000162
Figure GDA0003389845270000171
The comparison shows that the catalyst with the membrane coating structure has higher catalytic performance and good oxidation resistance under the same condition. After 4320h of air exposure oxidation, the catalyst still has high catalytic efficiency.
From the above reaction results, Mn is supported as carrier 3 (PO 4 ) 2 Co metal supported catalyst (Co/Mn) 3 (PO 4 ) 2 ) At 90 ℃ and 3MPa H 2 Under the condition, the effect is already optimal after the maleic anhydride is catalyzed for 5 hours; the effect is already optimal after the levulinic acid is catalyzed to react for 3.5 hours at 110 ℃ under the condition of 3MPa H2; the effect is already optimal after the benzaldehyde is catalyzed to react for 5 hours at the temperature of 90 ℃ and under the condition of 2.5MPa H2; at 120 ℃ and 3.5MPa H 2 Under the condition, the effect is optimal after the glucose is catalyzed for 8 hours; from the experimental results of the above examples, the catalyst with the membrane-coated structure has excellent acid resistance and oxidation resistance while having excellent catalytic performance.
Therefore, it is shown from the experimental results of the above examples that the present invention mainly makes the carrier Mn 3 (PO 4 ) 2 The phosphate catalyst prepared by the method of impregnation with metals such as Co, Pd and the like can achieve high conversion rate under quite mild conditions (>99%) high selectivity (>99%) to obtain succinic acid, gamma-valerolactone, benzyl alcohol and sorbitol. The method for preparing the large platform molecules such as the succinic acid, the gamma-valerolactone, the benzyl alcohol, the sorbitol and the like has the advantages of simple process, simple reaction equipment, simple and convenient operation, easy separation of products and catalysts, low price and easy obtainment of the catalysts, good hydrothermal stability and recycling performance of the catalysts, suitability for industrial production and very wide application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (9)

1. The application of the high-efficiency and high-stability nano catalyst with the film coating layer is characterized in that: the catalyst is applied to preparation of succinic acid by maleic anhydride hydrogenation, preparation of gamma-valerolactone by levulinic acid hydrogenation, preparation of benzyl alcohol by benzaldehyde hydrogenation or preparation of sorbitol by glucose hydrogenation; the catalyst is phosphate B (PO) 4 ) a As carrier in phosphate B (PO) 4 ) a The carrier is loaded with metal phosphide AP b Particles in metal phosphide AP b The surface of the particles is coated with BO c A film coating layer, wherein A is one or more transition metal elements in VIIIB, IB and IIB groups of the periodic table, B is one or more of yttrium (Y), titanium (Ti), manganese (Mn), lanthanum (La), chromium (Cr) and lead (Pb), and a, B and c independently take values under the condition of valence bond balance of a chemical formula; the catalyst is used for catalyzing maleic anhydride hydrogenation to prepare succinic acid, levulinic acid hydrogenation to prepare gamma-valerolactone, benzaldehyde hydrogenation to prepare benzyl alcohol or glucose hydrogenation to prepare sorbitol, and the reaction process comprises the following steps: adding maleic anhydride, levulinic acid, benzaldehyde or glucose and a catalyst into a reaction kettle together, and adding H 2 Washing the reaction kettle, replacing the air in the reaction kettle, and then keeping the reaction kettle in H 2 The pressure is 0.1 to 5MPa, the mixture is stirred and reacts for 2 to 15 hours at the temperature of between 0 and 180 ℃, and then the mixture is cooled and decompressed;
the catalyst is prepared by the following method:
step one, preparing a pre-salt carrier, namely sequentially and uniformly mixing soluble salt of B, citric acid, urea and diammonium hydrogen phosphate, and drying and calcining after hydrothermal treatment to obtain the pre-salt carrier;
secondly, loading, namely dissolving nitrate or acetate of the carrier A in acetone to prepare an acetone solution of the carrier A, and soaking the pre-salt carrier prepared in the first step in the acetone solution of the carrier A;
and step three, drying, calcining and reducing, namely taking out the pre-salt carrier treated in the step two, drying, calcining, and reducing in a hydrogen atmosphere to obtain the high-efficiency and high-stability nano catalyst with the film coating layer.
2. The use of a high efficiency, high stability nanocatalyst with a membrane coating as recited in claim 1, wherein: the A is one or more of palladium (Pd), iridium (Ir), platinum (Pt), nickel (Ni), copper (Cu) and cobalt (Co).
3. The use of a high efficiency, high stability nanocatalyst with a membrane coating as recited in claim 1, wherein: the concentration of the maleic anhydride, levulinic acid, benzaldehyde and glucose in the catalytic reaction is 0.5-1 wt%.
4. The use of a high efficiency, high stability nanocatalyst having a coating as recited in claim 1 wherein: the loading amount of the metal element B in the catalyst in the catalytic reaction is 1-15 wt%.
5. The use of a high efficiency, high stability nanocatalyst with a membrane coating as recited in claim 1, wherein: the reaction temperature in the reaction of preparing succinic acid by maleic anhydride hydrogenation is 30-150 ℃, the reaction temperature in the reaction of preparing gamma-valerolactone by levulinic acid hydrogenation is 30-160 ℃, the reaction temperature in the reaction of preparing benzyl alcohol by benzaldehyde hydrogenation is 30-140 ℃, and the reaction temperature in the reaction of preparing sorbitol by glucose hydrogenation is 0-180 ℃.
6. The use of a high efficiency, high stability nanocatalyst with a membrane coating as recited in claim 1, wherein: the catalyst is prepared by the following method:
step one, preparing a pre-salt carrier, namely mixing soluble salt B, citric acid, urea and diammonium hydrogen phosphate uniformly in sequence, and drying and calcining the mixture after hydrothermal treatment to obtain the pre-salt carrier;
secondly, loading, namely dissolving nitrate or acetate of the carrier A in acetone to prepare an acetone solution of the carrier A, and soaking the pre-salt carrier prepared in the first step in the acetone solution of the carrier A;
and step three, drying, calcining and reducing, namely taking out the pre-salt carrier treated in the step two, drying, calcining, and reducing in a hydrogen atmosphere to obtain the high-efficiency and high-stability nano catalyst with the film coating layer.
7. The use of a high efficiency, high stability nanocatalyst with a membrane coating as recited in claim 6, wherein: the concentration of the acetone solution of A is 3-12 mmol/L; the dipping time in the second step is 12-24 hours; in the third step, the drying temperature is 20-120 ℃, the drying time is 6-12 hours, the calcining temperature is 600 ℃, the calcining time is 2 hours, the reducing temperature is 600-.
8. The use of a high efficiency, high stability nanocatalyst with a membrane coating as recited in claim 6, wherein: step one the preparation method of the pre-salt carrier is as follows: adding soluble salt B into a hydrothermal kettle, adding water, stirring to dissolve the soluble salt B, sequentially adding citric acid, urea and diammonium hydrogen phosphate under a stirring state, transferring the hydrothermal kettle into an oven to perform hydrothermal reaction after stirring is finished, and filtering, drying and calcining after the hydrothermal reaction is finished to obtain a salt carrier; the molar ratio of the soluble salt of B, citric acid, urea and diammonium hydrogen phosphate is 1: 3: 6: 1 to 5.
9. The use of a high efficiency, high stability nanocatalyst having a coating as recited in claim 6 wherein: in the specific method for preparing the salt carrier, each substance is sequentially added, the stirring interval time is 15 minutes, the diammonium hydrogen phosphate is added, the stirring is continued for 15 minutes, then the mixture is moved into an oven for hydrothermal reaction, the temperature of the hydrothermal reaction is 160 ℃, the time is 13 hours, the drying temperature is 105 ℃, the calcining temperature is 550 ℃, and the calcining time is 2 hours.
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