Preparation of reverse catalyst and application of reverse catalyst in preparation of polyol by catalyzing hydrogenolysis of biomass derivative
By loading the reverse phase catalyst of nanometal oxide on the support metal, using interfacial electron interaction, the problems of poor selectivity of polyols and unstable catalysts in the prior art are solved, and efficient conversion of bio-based derivatives is achieved and high selection is generated. and improve catalyst performance.
Patent Information
- Application Number
- CN202411270978.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-11
- Publication Date
- 2024-12-06
AI Technical Summary
When the existing precious metal catalysts prepare polyols by catalyzing the hydrogenolysis of biomass derivatives, there are problems with poor selectivity of the polyol and catalyst instability, and the high cost limits their application.
Develop a cheap inverted MOx/M' catalyst to form a nano-oxide/metal inverted interface structure by uniformly loading nano-metal oxide MO on the support metal M', and use strong interfacial electron interaction to promote biomass The C-O bond cleavage and hydrogenation reaction in derivatives can prepare highly selective polyols.
It realizes efficient conversion of bio-based derivatives under relatively mild conditions to generate highly selective polyols, expands the application range of bio-based derivatives, and improves the stability and performance of the catalyst.
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Figure CN119076002A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of biomass conversion catalysts, and particularly relates to a reverse catalyst and application of the catalyst in catalyzing the hydrogenolysis of biomass derivatives to prepare polyols. Background Art
[0002] Biomass-derived molecules contain different CO bonds, such as ether / furan CO bonds in cellulose and hemicellulose derivatives, and phenolic CO bonds in lignin components. Although the development of noble metal (Ir, Pd, Ru, and Rh) catalysts in recent decades has effectively improved the catalytic performance of such reactions by introducing nano-metal oxides MO (M = Re, Mo, W, and V), MO promotes further hydrodeoxygenation of polyols to form byproducts, resulting in such reactions only having ideal polyol selectivity at low conversion rates. In addition, the high cost of the catalysts and the decreased stability caused by MO leaching also limit their application. Therefore, it is of great practical value to develop an efficient and long-lived non-noble metal catalyst for the hydrogenolysis of biomass derivatives to prepare polyols. Summary of the invention
[0003] The main purpose of the present invention is to provide a cheap reverse MOx / M' catalyst and the use of the catalyst for catalyzing the hydrogenolysis of biomass derivatives to prepare polyols. The reverse MOx / M' catalyst of the present invention exhibits different selectivity from traditional catalysts when catalyzing the hydrogenolysis of biomass derivatives, especially being able to generate important polyols with high selectivity.
[0004] The reverse phase catalyst provided by the present invention is a nano-metal oxide MO as a supporting phase uniformly supported on a carrier metal M' to form a nano-oxide / metal reverse phase interface structure, which is recorded as MOx / M', and x represents the molar ratio of M' to M; wherein the nano-metal oxide MO is one of molybdenum oxide, rhenium oxide, tin oxide, yttrium oxide or lanthanide metal oxide, and the carrier metal M' is one of ruthenium, cobalt, platinum, nickel, palladium, copper or silver.
[0005] In the catalyst, the molar ratio of M' to M is 5-320:1.
[0006] The preparation method of the reverse phase catalyst comprises the following steps: dripping an aqueous solution of a carrier metal M' precursor and a nano metal oxide MO precursor into a precipitant under vigorous stirring, continuously stirring and mixing the mixture evenly, sealing the mixture in a hydrothermal kettle, heating the mixture to 100-200° C., and performing a hydrothermal reaction for 12-48 hours; filtering the mixture after the reaction, washing the mixture, and drying the mixture in an environment of 60-120° C.; then calcining the dried sample at 300-600° C. in an air atmosphere for 2-8 hours, and reducing the calcined sample in a hydrogen atmosphere at 250-550° C. for 2-6 hours to obtain a reverse phase catalyst MOx / M'.
[0007] The carrier metal M' precursor is selected from one or two of chlorides, sulfates, nitrates, phosphates, acetates and hydrates of ruthenium, cobalt, platinum, nickel, palladium, copper and silver, and the nano metal oxide MO precursor is selected from one or two of chlorides, sulfates, nitrates, phosphates, acetates and hydrates of molybdenum, rhenium, tin, yttrium and lanthanide metals.
[0008] The precipitant is an aqueous solution of one or more of potassium carbonate, potassium bicarbonate, tetramethylammonium hydroxide, sodium hydroxide, oxalic acid, sodium carbonate, potassium hydroxide, sodium bicarbonate, tetraethylammonium hydroxide, urea, ammonium carbonate, and ammonia water.
[0009] The invention discloses an application of the reverse phase catalyst in catalyzing the hydrogenolysis of biomass derivatives to prepare polyols.
[0010] The reaction of preparing polyols by hydrogenolysis of biomass derivatives is carried out in an intermittent reactor, the H2 pressure in the reaction is 1-5 MPa, the reaction temperature is 120-200°C, the reaction system is a solvent-free system or a solvent system, and the solvent is one of methanol, ethanol, isopropanol, and tetrahydrofuran.
[0011] The reaction of preparing polyols by hydrogenolysis of biomass derivatives is carried out in a continuous fixed bed reactor, and the H2 pressure in the reaction is 1-5 MPa and the flow rate is 30-60 mL·min –1 , the reaction temperature is 120~200℃.
[0012] The biomass derivative is one of furfural, tetrahydrofurfural, furfuryl alcohol, tetrahydrofurfuryl alcohol, 5-hydroxymethylfurfural, 5-hydroxymethylfurfuryl alcohol, and 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenyl)-propane-1,3-diol.
[0013] The reverse phase catalyst of the present invention has the characteristics of selectively breaking carbon-oxygen bonds and selectively hydrogenating. It can utilize the strong interfacial electronic interaction between MO and M' to enhance the adsorption of ether oxygen on the electron-rich interface near the oxygen vacancy, promote the cleavage of the CO bond in the biomass derivative molecule, and obtain highly selective polyols.
[0014] The present invention has the following advantages over the prior art: 1. The present invention solves the problems of poor polyol selectivity and unstable catalyst in the prior art by constructing an anti-phase interface between MO and M' active components to form a strong interfacial electronic interaction; 2. The present invention achieves efficient conversion of bio-based derivatives under relatively mild and environmentally friendly conditions, and the produced polyol compounds are polymer monomers, which expands the application scope of bio-based derivatives. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Figure 1 This is the XRD picture of the reverse SnO2 / Cu catalyst prepared in Example 1 of the present invention. Figure 2 This is an XPS photo of the reverse SnO2 / Cu catalyst prepared in Example 1 of the present invention. Figure 3 This is the XRD photograph of the inverse HoO2 / Ni catalyst prepared in Example 2 of the present invention. Figure 4 This is the XPS photograph of the inverse HoO2 / Ni catalyst prepared in Example 2 of the present invention. DETAILED DESCRIPTION
[0016] The present invention is further described in detail below through specific examples, but the protection scope of the present invention is not limited to these examples. The experimental methods used in the examples are conventional methods unless otherwise specified; the materials, reagents, etc. used in the examples, unless otherwise specified, can be obtained from commercial channels.
[0017] Example 1 Preparation of reverse SnO2 / Cu catalyst (Cu to Sn molar ratio of 80): 19.3g Cu(NO3)2·3H2O aqueous solution and 0.35g SnCl4·5H2O aqueous solution were added dropwise to sodium hydroxide aqueous solution under vigorous stirring, and stirring was continued for 1 hour. The mixed solution was placed in a hydrothermal kettle, hydrothermal at 110℃ for 48h, filtered, washed with water, dried, calcined at 600℃ in air for 5h, and then reduced at 350℃ in hydrogen for 4h to obtain reverse SnO2 / Cu catalyst. The prepared reverse SnO2 / Cu catalyst was proved by XRD and XPS characterization. The results are as follows Figure 1 and 2 shown. Figure 1 This is the XPS spectrum of Cu. It can be seen that there are two diffraction peaks at 933eV and 952.3eV, corresponding to Cu2p 3 / 2 and Cu2p 1 / 2 , indicating that copper exists in zero-valent and positive-one-valent forms; Figure 2 The XRD results showed only the diffraction peak of copper, and no diffraction peak of SnO2 was found, indicating that the SnO2 particles were evenly dispersed and had a small particle size.
[0018] Example 2 Preparation of reversed HoO2 / Ni (Ni to Ho molar ratio of 320) catalyst: Under vigorous stirring, 23.3g Ni(NO3)2·6H2O aqueous solution and 0.11g Ho(NO3)3·6H2O aqueous solution were added dropwise to oxalic acid aqueous solution, and stirring was continued for 2 hours. The mixed solution was charged into a hydrothermal kettle, hydrothermal at 150°C for 24 hours, filtered, washed with water, dried, calcined at 500°C in air for 5 hours, and then reduced at 450°C in hydrogen for 3 hours to obtain reversed HoO2Ni. The prepared reversed HoO2 / Ni catalyst was confirmed by XRD and XPS characterization. The results are as follows Figure 3 and 4 shown. Figure 3 The XRD results showed only the diffraction peak of nickel, but no diffraction peak of HoO2, indicating that the HoO2 particles were evenly dispersed and had a small particle size. Figure 4 The results show that nickel is mainly present in the zero-valent form.
[0019] Example 3 Preparation of reversed La2O3 / Ag (Ag to La molar ratio is 160) catalyst: Under vigorous stirring, 13.6g AgNO3 aqueous solution and 0.22g La(NO3)3·6H2O aqueous solution were added dropwise to tetramethylammonium hydroxide solution, and stirring was continued for 1 hour. The mixed solution was charged into a hydrothermal kettle, hydrothermaled at 100℃ for 24h, filtered, washed with water, dried, calcined at 400℃ in air for 6h, and then reduced at 300℃ in hydrogen for 3h to obtain reversed La2O3 / Ag.
[0020] Example 4 Preparation of reverse CeO2 / Co (Co to Ce molar ratio is 20) catalyst: Under vigorous stirring, 22.5g CoSO4·7H2O aqueous solution and 1.72g Ce(NO3)3·6H2O aqueous solution were added dropwise to the oxalic acid aqueous solution, and stirring was continued for 1 hour. The mixed solution was charged into a hydrothermal autoclave, hydroheated at 140℃ for 24h, filtered, washed with water, dried, calcined at 400℃ in air for 3h, and then reduced at 350℃ in hydrogen for 3h to obtain the reverse CeO2 / Co catalyst.
[0021] Example 5 Inverted YO x Preparation of Ru / Ru (Ru to Y molar ratio is 20) catalyst: 12.4 g RuCl·xH2O aqueous solution and 0.798 g Y(NO3)3·xH2O aqueous solution were added dropwise to oxalic acid aqueous solution under vigorous stirring, and stirring was continued for 1 hour. The mixed solution was placed in a hydrothermal kettle, hydrothermal at 140°C for 24 hours, filtered, washed with water, dried, calcined at 400°C in air for 3 hours, and then reduced at 350°C in hydrogen for 3 hours to obtain reversed YO x / Ru catalyst.
[0022] Example 6 The reverse SnO2 / Cu catalyst (Cu to Sn molar ratio of 80) prepared in Example 1 was used to catalyze the hydrogenolysis reaction of tetrahydrofurfuryl alcohol. The specific reaction method is as follows: 0.25 g of catalyst and 0.5 g of tetrahydrofurfuryl alcohol were added to a 100 mL stainless steel reactor, the reactor was closed, and the gas in the reactor was replaced with hydrogen five times. 4 MPa of hydrogen was filled into the reactor at room temperature before the reaction. The reactor was heated to 160°C and the reaction was started. After 12 hours of reaction, the reactor was placed in an ice water bath for cooling, the hydrogen was vented, and the liquid was analyzed in a gas chromatograph after centrifugal separation. The results are shown in Table 1.
[0023] Example 7 The reverse SnO2 / Cu catalyst (Cu to Sn molar ratio of 80) prepared in Example 1 was used to catalyze the hydrogenolysis reaction of 5-hydroxymethylfurfural. The specific reaction method is as follows: 0.25 g of catalyst and 0.5 g of 5-hydroxymethylfurfural were added to a 100 mL stainless steel reactor, the reactor was closed, the gas in the reactor was replaced with hydrogen five times, 4 MPa of hydrogen was filled at room temperature before the reaction, the reactor was heated to 160°C, the reaction was started, and after 10 hours of reaction, the reactor was placed in an ice water bath to cool, the hydrogen was vented, and the liquid was analyzed in a gas chromatograph after centrifugal separation. The results are shown in Table 1.
[0024] Example 8 The reverse SnO2 / Cu catalyst (Cu to Sn molar ratio of 80) prepared in Example 1 was used to catalyze the hydrogenolysis reaction of 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenyl)-propane-1,3-diol. The specific reaction method is as follows: 0.12g of catalyst and 0.25g of 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenyl)-propane-1,3-diol were added to a 100mL stainless steel reactor, the reactor was closed, and the gas in the reactor was replaced with hydrogen five times. 4MPa of hydrogen was filled at room temperature before the reaction, and the reactor was heated to 160°C to start the reaction. After 24 hours of reaction, the reactor was placed in an ice water bath to cool, the hydrogen was vented, and the liquid was analyzed in a gas chromatograph after centrifugal separation. The results are shown in Table 1.
[0025] Example 9 The reverse SnO2 / Cu catalyst (Cu to Sn molar ratio of 80) prepared in Example 1 was used to catalyze the hydrogenolysis reaction of furfuryl alcohol. The specific reaction method is as follows: 2.0 g of the catalyst prepared above was loaded into a continuous tubular reactor, filled with 6.0 MPa of hydrogen, and heated to 180°C. Furfuryl alcohol was continuously injected into the reactor using a high-pressure injection pump at an air velocity of 0.2 g / gh. The reaction liquid was collected in the liquid storage tank of the device and subjected to chromatographic analysis.
[0026] Table 1 Hydrogenolysis results of different biomass derivatives using reversed SnO2 / Cu catalyst .
[0027] Comparative Example 1 Preparation of traditional Cu / SnO2 (Cu to Sn molar ratio of 1:9.5): Under vigorous stirring, 1.12g Cu(NO3)2·3H2O aqueous solution and 17.2g SnCl4·5H2O aqueous solution were added dropwise to the oxalic acid aqueous solution, and stirring was continued for 1 hour. The mixed solution was charged into a hydrothermal kettle, hydroheated at 140℃ for 24h, filtered, washed with water, dried, calcined at 400℃ in air for 3h, and then reduced at 350℃ in hydrogen for 3h to obtain the traditional Cu / SnO2 catalyst.
[0028] Comparative Example 2 The conventional Cu / SnO2 catalyst prepared in Comparative Example 1 was used to catalyze the hydrogenolysis reaction of tetrahydrofurfuryl alcohol, and the specific hydrogenation reaction method was the same as that in Example 5. The results are shown in Table 2.
[0029] Comparative Example 3 The conventional Cu / SnO2 catalyst prepared in Comparative Example 1 was used to catalyze the hydrogenolysis reaction of 5-hydroxymethylfurfural, and the specific hydrogenation reaction method was the same as that in Example 6. The results are shown in Table 2.
[0030] Comparative Example 4 The conventional Cu / SnO2 catalyst prepared in Comparative Example 1 was used to catalyze the hydrogenolysis reaction of 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenyl)-propane-1,3-diol, and the specific hydrogenation reaction method was the same as that in Example 7. The results are shown in Table 2.
[0031] Table 2 Hydrogenolysis results of Cu / SnO2 catalyst for different biomass derivatives From the comparison between Tables 1 and 2, it can be seen that the performance of the reverse catalyst is much higher than that of the conventional catalyst. The reason is that the strong interfacial electronic interaction between the metal oxide and the metal of the reverse catalyst enhances the adsorption of ether oxygen on the electron-rich interfacial sites near the oxygen vacancies, promotes the cleavage of the CO bond in the biomass derivative molecules, and improves the performance of the catalyst.
Claims
1. A reverse phase catalyst, characterized in that: Nano-metal oxide MO is used as a loading phase and is uniformly loaded on a carrier metal M' to form a nano-oxide / metal reverse interface structure, which is recorded as MOx / M', and x represents the molar ratio of M' to M; wherein the nano-metal oxide MO is one of molybdenum oxide, rhenium oxide, tin oxide, yttrium oxide or lanthanide metal oxide, and the carrier metal M' is one of ruthenium, cobalt, platinum, nickel, palladium, copper or silver.
2. A reverse phase catalyst as claimed in claim 1, characterized in that: The molar ratio of M' to M is 5-320:
1.
3. A method for preparing a reverse phase catalyst as claimed in claim 1, characterized in that: Under vigorous stirring, an aqueous solution of a carrier metal M' precursor and a nano metal oxide MO precursor is dropped into a precipitant, and after continuous stirring and mixing, the mixture is sealed in a hydrothermal kettle and heated to 100-200°C for a hydrothermal reaction for 12-48 hours. After the reaction is completed, the mixture is filtered, washed, and dried. The dried sample is then calcined at 300-600°C in an air atmosphere for 2-8 hours, and the calcined sample is placed in a hydrogen atmosphere for reduction at 250-550°C for 2-6 hours to obtain a reverse catalyst MOx / M'.
4. The method for preparing a reverse phase catalyst as claimed in claim 3, characterized in that: The carrier metal M' precursor is selected from one or two of chlorides, sulfates, nitrates, phosphates, acetates and hydrates of ruthenium, cobalt, platinum, nickel, palladium, copper and silver, and the nano metal oxide MO precursor is selected from one or two of chlorides, sulfates, nitrates, phosphates, acetates and hydrates of molybdenum, rhenium, tin, yttrium and lanthanide metals.
5. The method for preparing a reverse phase catalyst as claimed in claim 3, characterized in that: The precipitant is an aqueous solution of one or more of potassium carbonate, potassium bicarbonate, tetramethylammonium hydroxide, sodium hydroxide, oxalic acid, sodium carbonate, potassium hydroxide, sodium bicarbonate, tetraethylammonium hydroxide, urea, ammonium carbonate, and ammonia water.
6. Use of the reverse phase catalyst as claimed in claim 1 in catalyzing the hydrogenolysis of biomass derivatives to prepare polyols.
7. Use of the reverse phase catalyst as claimed in claim 6 in catalyzing the hydrogenolysis of biomass derivatives to prepare polyols, characterized in that: The reaction of preparing polyols by hydrogenolysis of biomass derivatives is carried out in an intermittent reactor, the H2 pressure in the reaction is 1-5 MPa, the reaction temperature is 120-200°C, the reaction system is a solvent-free system or a solvent system, and the solvent is one of methanol, ethanol, isopropanol, and tetrahydrofuran.
8. Use of the reverse phase catalyst as claimed in claim 6 in catalyzing the hydrogenolysis of biomass derivatives to prepare polyols, characterized in that: The reaction of preparing polyols by hydrogenolysis of biomass derivatives is carried out in a continuous fixed bed reactor, and the H2 pressure in the reaction is 1-5 MPa and the flow rate is 30-60 mL·min –1 , the reaction temperature is 120~200℃.
9. Use of the reverse phase catalyst as claimed in claim 6 in catalyzing the hydrogenolysis of biomass derivatives to prepare polyols, characterized in that: The biomass derivative is one of furfural, tetrahydrofurfural, furfuryl alcohol, tetrahydrofurfuryl alcohol, 5-hydroxymethylfurfural, 5-hydroxymethylfurfuryl alcohol, and 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenyl)-propane-1,3-diol.