CN115814814B - Preparation method of ruthenium-loaded iron-chromium bimetallic oxide catalyst and method for synthesizing 2,5-furandicarboxylic acid using the catalyst - Google Patents
Preparation method of ruthenium-loaded iron-chromium bimetallic oxide catalyst and method for synthesizing 2,5-furandicarboxylic acid using the catalyst Download PDFInfo
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Abstract
一种负载钌的铁铬双金属氧化物催化剂制备方法及应用该催化剂合成2,5‑呋喃二甲酸的方法，属于催化剂制备及应用技术领域。本发明利用水热‑煅烧法制备铁铬双金属氧化物作为催化剂载体，利用浸渍‑还原法在载体上负载少量钌纳米粒子作为活性组分，通过活性组分与载体之间的协同作用实现了5‑羟甲基糠醛的高效选择性催化合成2,5‑呋喃二甲酸。本发明的催化剂制备过程简单，易放大，在温和的条件下，5‑羟甲基糠醛的转化率为100％，2,5‑呋喃二甲酸的产率为99.9％，收集反应后滤液经提纯获得的白色粉末状2,5‑呋喃二甲酸纯度大于99％，该工艺路线具有光明的2,5‑呋喃二甲酸产业化生产前景。
A method for preparing a ruthenium-loaded iron-chromium bimetallic oxide catalyst and a method for synthesizing 2,5-furandicarboxylic acid using the catalyst belong to the technical field of catalyst preparation and application. The present invention utilizes a hydrothermal calcination method to prepare an iron-chromium bimetallic oxide as a catalyst carrier, utilizes an impregnation reduction method to load a small amount of ruthenium nanoparticles on the carrier as an active component, and realizes the efficient and selective catalytic synthesis of 2,5-furandicarboxylic acid of 5-hydroxymethylfurfural through the synergistic effect between the active component and the carrier. The catalyst preparation process of the present invention is simple and easy to enlarge. Under mild conditions, the conversion rate of 5-hydroxymethylfurfural is 100%, the yield of 2,5-furandicarboxylic acid is 99.9%, and the purity of the white powdery 2,5-furandicarboxylic acid obtained by collecting the filtrate after the reaction and purifying is greater than 99%. The process route has a bright prospect for the industrialization and production of 2,5-furandicarboxylic acid.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and application, and particularly relates to a preparation method of a ruthenium-supported iron-chromium bimetallic oxide catalyst and a method for synthesizing 2, 5-furandicarboxylic acid by using the catalyst.
Background
The 2, 5-furandicarboxylic acid converted from the biomass platform compound 5-hydroxymethylfurfural can be used for synthesizing various fine chemicals and furanyl polymers, and is a novel bio-based monomer which is important and has wide application prospect. The molecular structure of the 2, 5-furandicarboxylic acid contains furan rings, so that the heat resistance and the mechanical property of the polymer material can be effectively improved when the polymer material is synthesized, and the polymer material can replace Petrochemical Terephthalic Acid (PTA) to produce biodegradable and excellent bio-based Polyester (PEF), thereby being used for synthesizing fibers, films, engineering plastics and the like.
The 5-hydroxymethylfurfural oxidation route is considered as the route most promising for mass production of 2, 5-furandicarboxylic acid. There has been a great deal of research on the use of bimetallic oxides as catalysts in the oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid. Literature reports Gawade et al, which are used for preparing MnFe 2O4 magnetic nano particles with spinel structures, acetonitrile is used as a solvent, tert-butyl hydroperoxide is used as an oxidant, and the reaction is carried out for 5 hours at the temperature of 100 ℃, so that the yield of 2, 5-furandicarboxylic acid reaches 85%. Zhao et al synthesized a series of Fe xZr1-xO2 catalysts by hydrothermal method, among which Fe 0.6Zr0.4O2 showed the best catalytic effect, after 24h reaction at 160℃under 2.0MPa O 2 and alkali-free conditions, the conversion of 5-hydroxymethylfurfural in ionic liquid [ Bmim ] Cl was 99.7% and the yield of 2, 5-furandicarboxylic acid was 60.6%.
In order to facilitate large-scale industrial production in the future, many researchers use green and environment-friendly water as a solvent and oxygen as an oxidant. Literature reports that Han et al prepared a series of MnO x-CeO2 catalysts by coprecipitation under 2.0MPa O 2 using 0.1g Mn/Ce molar ratio 6, reacted in KHCO 3 aqueous solution at 75℃for 15h followed by 110℃for 6h, with a conversion of 98% for 5-hydroxymethylfurfural and a yield of up to 91% for 2, 5-furandicarboxylic acid. Yu et al doped Ni, co, fe with MnO x nanowires, wherein Ni-MnO x had the best catalytic activity, and reacted in aqueous NaHCO 3 at 100deg.C under 0.8MPa O 2 for 28h to obtain 100% conversion of 5-hydroxymethylfurfural and 93.8% yield of 2, 5-furandicarboxylic acid. Zhang et al prepared a series of Mn-Co-O bimetallic catalysts of varying Mn/Co ratios using a hydrothermal process. Wherein, when the Mn/Co molar ratio is 0.5, the catalytic effect is optimal. In KHCO 3 aqueous solution, the conversion rate of 5-hydroxymethylfurfural is 99.5% and the yield of 2, 5-furandicarboxylic acid is 70.9% after the reaction is carried out at 100 ℃ and 1.0MPa O 2.
In order to further improve the catalytic activity of the bimetallic oxide catalyst in the aqueous solution, researchers have carried a small amount of noble metal as an active component by using the bimetallic oxide as a carrier, and Ru is cheaper among the noble metals. Antonyraj et al prepared the catalyst by using MgAlO as the carrier and Ru, and reacted in aqueous solution at 140℃and 90psi O 2 for 4 hours to obtain 100% conversion of 5-hydroxymethylfurfural and 99% yield of 2, 5-furandicarboxylic acid. However, ru/MgAlO is easy to be seriously dissolved in the reaction process, so that the catalyst is difficult to realize repeated use. Mishra et al use MnCo 2O4 as a carrier to load Ru to prepare a catalyst Ru/MnCo 2O4, and react for 10 hours under the conditions of taking water as a solvent, 2.4MPa air and 120 ℃, wherein the conversion rate of 5-hydroxymethylfurfural reaches 100%, and the yield of 2, 5-furandicarboxylic acid reaches 99.1%. By comparison, the catalytic performance of Ru/MnCo 2O4 is superior to that of MnCo 2O4 without Ru, and the Ru is proved to be an active center of the catalyst and has synergistic effect with a MnCo 2O4 carrier.
The bimetallic oxide and Ru-loaded bimetallic oxide applied to the reaction have been reported to have the problems of complex catalyst preparation process, easy deactivation of the catalyst, overhigh reaction pressure, improved catalytic activity, difficult product separation and the like. Therefore, the development of the catalyst with high activity and high stability realizes the efficient synthesis of the 2, 5-furandicarboxylic acid by the 5-hydroxymethylfurfural in an environment-friendly, simple and green catalytic system, so that the technology for synthesizing the 2, 5-furandicarboxylic acid gradually advances to industrial production, and the catalyst has great application prospect and social significance in the future. Up to now, the reaction research of using Fe-Cr bimetallic oxide as a catalyst of supporting ruthenium and for synthesizing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural has not been reported.
There is a need in the art for a new solution to this problem.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the preparation method of the iron-chromium bimetallic oxide catalyst loaded with ruthenium and the method for synthesizing 2, 5-furandicarboxylic acid by using the catalyst are used for solving the problems that the existing bimetallic oxide and the bimetallic oxide loaded with Ru have complex catalyst preparation process, easy deactivation of the catalyst, overhigh reaction pressure, improved catalytic activity and difficult product separation; up to now, the reaction research of using the iron-chromium bimetallic oxide as a catalyst of supporting ruthenium and for synthesizing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural has not been reported.
The preparation method of the iron-chromium bimetallic oxide catalyst loaded with ruthenium comprises the following steps in sequence:
step one, preparing a precursor mixed solution:
Dissolving Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O in deionized water according to a selected molar ratio, and dropwise adding a sodium hydroxide aqueous solution into the solution under the condition of stirring at 500rpm until the PH is 9-11, and stopping dropwise adding to obtain a precursor ferrochrome hydroxide mixed solution;
Step two, preparing a carrier:
placing the precursor iron-chromium hydroxide mixed solution in a hydrothermal kettle for hydrothermal treatment, after the hydrothermal treatment is finished and cooled to room temperature, filtering and washing the precipitate to be neutral, drying to obtain precursor powder, calcining the precursor powder in an air atmosphere, and cooling to room temperature to obtain an iron-chromium bimetallic oxide carrier;
Step three, loading active components:
And (3) weighing deionized water, dissolving RuCl 3·3H2 O in the deionized water, weighing an iron-chromium bimetallic oxide carrier, dispersing the carrier in the deionized water, then soaking and dispersing in an ice water bath under a stirring state to obtain a dispersion liquid, dropwise adding an aqueous solution of NaBH 4 containing NaOH into the dispersion liquid under the stirring condition of the ice water bath, continuously stirring and reducing, filtering and washing a precipitate to be neutral, and carrying out vacuum drying to obtain the ruthenium-loaded iron-chromium bimetallic oxide catalyst.
In the first step, fe (the molar ratio of NO 3)3·9H2 O to Cr (NO 3)3·9H2 O) is respectively 0:1, 1:2, 2:1 and 1:0, the carriers prepared in the second step are respectively named Cr1-Fe0-O, cr2-Fe1-O, cr-Fe 2-O and Cr0-Fe1-O, and the catalysts obtained in the third step are respectively named Ru/Cr1-Fe0-O, ru/Cr2-Fe1-O, ru/Cr1-Fe2-O and Ru/Cr0-Fe1-O.
In the first step, the specific conditions of Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O dissolved in deionized water) are that Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O) are dissolved in 60mL of deionized water by 6mmol in total, and the concentration of the sodium hydroxide aqueous solution is 1.0 mol/L-2.0 mol/L.
The specific conditions of the hydrothermal process in the second step are as follows: the hydrothermal temperature is 160-200 ℃, and the hydrothermal time is 3-6 h;
the specific conditions for calcination are: the calcination temperature is 350-500 ℃ and the calcination time is 2-6 h;
The specific conditions for drying are as follows: the drying temperature is 50-120 ℃, and the drying time is 8-24 hours.
And step three, weighing 12.5mL of deionized water, weighing 0.5g of the iron-chromium bimetallic oxide carrier, and adding 0.0259 g-0.0518 g of RuCl 3·3H2 O, wherein the load of ruthenium accounts for 2-4wt% of the carrier.
The concentration of the NaOH aqueous solution in the third step is 0.25-0.75 wt%, the concentration of NaBH 4 is 1.0-2.0 mol/L, and the molar ratio of BH 4 -in NaBH 4 to Ru 3+ in RuCl 3·3H2 O is 10:1-30:1.
In the third step, the dipping and dispersing time is 8-24 h, the stirring and reducing time is 8-24 h, the drying temperature of vacuum drying is 50-120 ℃ and the drying time is 8-24 h.
The method for synthesizing 2, 5-furandicarboxylic acid by using the ruthenium-loaded iron-chromium bimetallic oxide catalyst comprises the following steps of:
Step one, oxidizing 5-hydroxymethylfurfural:
Adding 5-hydroxymethylfurfural, deionized water, ruthenium-loaded iron-chromium bimetallic oxide catalyst and KHCO 3 into a reaction kettle, introducing oxygen into the reaction kettle after the reaction kettle is installed, reacting under the condition of heating and stirring, stopping heating to reduce the temperature to room temperature, exhausting gas, filtering out the catalyst, diluting the reaction liquid with purified water, and analyzing the diluted reaction liquid by using a high performance liquid chromatograph, thereby calculating the conversion rate of 5-hydroxymethylfurfural and the yield of 2, 5-furandicarboxylic acid;
step two, purifying 2, 5-furandicarboxylic acid:
Collecting filtrate obtained after the reaction, removing water, adding concentrated hydrochloric acid until the pH is less than 1, crystallizing and separating 2, 5-furandicarboxylic acid from the filtrate, filtering, washing with water, drying to obtain white powdery 2, 5-furandicarboxylic acid, dissolving the obtained white powdery product in purified water, and analyzing by using a high performance liquid chromatograph, thereby calculating the purity of the 2, 5-furandicarboxylic acid.
The usage amount of the 5-hydroxymethylfurfural, deionized water, ruthenium-loaded iron-chromium bimetallic oxide catalyst and KHCO 3 and the reaction conditions are as follows:
dissolving 0.2mmol of 5-hydroxymethylfurfural in 5mL of deionized water, wherein the reaction temperature is 80-120 ℃, the reaction time is 12-24 h, the oxygen pressure is 0.5-1.5 MPa, the dosage of the iron-chromium bimetallic oxide catalyst loaded with ruthenium is 0.05-0.15 g, and the dosage of KHCO 3 is 0-0.06 g.
Through the design scheme, the invention has the following beneficial effects:
(1) The invention prepares the iron-chromium bimetallic oxide catalyst by using a hydrothermal-calcining method as a catalyst carrier, and loads a small amount of ruthenium nano particles as an active component on the carrier by using an impregnation-reduction method, so that the iron-chromium bimetallic oxide catalyst loaded with ruthenium is prepared, and the preparation process is simple and easy to amplify. The active center of the catalyst is Ru 0, and the interaction between the active component and the carrier is important to realize the high-efficiency catalysis of HMF.
(2) The iron-chromium bimetallic oxide catalyst loaded with ruthenium oxidizes 5-hydroxymethylfurfural under the condition of weak alkali aqueous solution, 1.0MPa of oxygen is filled into a reaction kettle, the reaction is carried out at 100 ℃ for 24 hours, the conversion rate of the 5-hydroxymethylfurfural is 100%, the yield of 2, 5-furandicarboxylic acid can reach 99.9%, and the purity of white powdery 2, 5-furandicarboxylic acid obtained by purifying filtrate after the collection reaction is more than 99%. Compared with other reported bimetallic oxides or bimetallic oxide supported ruthenium catalysts, the reaction temperature and the reaction pressure required by the reaction are lower, and the prepared catalyst not only has higher catalytic activity but also can be recycled, and has good application prospect in the field of catalysis.
Drawings
The invention is further described with reference to the drawings and detailed description which follow:
FIG. 1 is an X-ray diffraction pattern of a series of supports Cr1-Fe0-O, cr2-Fe1-O, cr1-Fe2-O and Cr0-Fe1-O prepared according to the present invention.
FIG. 2 is an X-ray photoelectron spectrum of a Ru/Cr2-Fe1-O catalyst supporting 4wt% ruthenium prepared in example 2 of the present invention.
FIG. 3 is an EDS spectrum of a Ru/Cr2-Fe1-O catalyst supporting 4wt% ruthenium prepared according to example 2 of the present invention.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
The preparation method of the iron-chromium bimetallic oxide catalyst loaded with ruthenium uses a hydrothermal-calcining method to prepare the iron-chromium bimetallic oxide as a catalyst carrier, and uses an impregnation-reduction method to load a small amount of ruthenium nano particles as an active component on the carrier, and comprises the following specific steps in sequence:
Preparing a precursor mixed solution: fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O) are dissolved in deionized water, and under the condition of intense stirring, a sodium hydroxide aqueous solution is dropwise added into the solution until the PH is approximately equal to 10, and the dropwise addition is stopped, so that a precursor ferrochrome hydroxide mixed solution is obtained.
And (3) preparing a carrier: and (3) placing the precursor iron-chromium hydroxide mixed solution in a hydrothermal kettle for hydrothermal treatment, cooling the hydrothermal treatment to room temperature, filtering, washing to neutrality, and drying to obtain precursor powder. And calcining the precursor powder in an air atmosphere, and cooling to room temperature to obtain the iron-chromium bimetallic oxide carrier.
Loading active components: ruCl 3·3H2 O is dissolved in deionized water, and the iron-chromium bimetallic oxide carrier is dispersed in the deionized water, and is immersed and dispersed in an ice-water bath under the stirring state. Then dropwise adding NaBH 4 aqueous solution containing NaOH into the dispersion liquid under the stirring condition of ice water bath, and continuing stirring and reduction. Filtering, washing to neutrality, and vacuum drying to obtain the Fe-Cr bimetallic oxide catalyst with ruthenium.
Preferably, in order to compare the catalytic effect with the ruthenium-supported single metal oxide catalyst prepared by the same method, fe (NO 3)3·9H2 O and Cr (the molar ratio of NO 3)3·9H2 O is 0:1, 1:2, 2:1 and 1:0) is selected in the preparation process of the precursor mixed solution, the corresponding carriers are named Cr1-Fe0-O, cr2-Fe1-O, cr1-Fe2-O and Cr0-Fe1-O, and the corresponding catalysts are named Ru/Cr1-Fe0-O, ru/Cr2-Fe1-O, ru/Cr1-Fe2-O and Ru/Cr0-Fe1-O.
Preferably, during the preparation of the precursor mixture, a total of 6mmol of Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O dissolved in 60mL of deionized water) and the concentration of the aqueous NaOH solution are 1.0mol/L to 2.0mol/L.
Preferably, in the carrier preparation process, the hydrothermal temperature is 160-200 ℃, the hydrothermal time is 3-6 h, the calcination temperature is 350-500 ℃, the calcination time is 2-6 h, the drying temperature is 50-120 ℃, and the drying time is 8-24 h.
Preferably, in the process of loading the active component, 0.5g of carrier is weighed and dispersed in 12.5mL of deionized water, the addition amount of RuCl 3·3H2 O is 0.0259 g-0.0518 g, and after the active component is loaded, the load amount of ruthenium accounts for 2wt% to 4wt% of the carrier.
Preferably, the molar ratio of BH 4 -in NaBH 4 to Ru 3+ in RuCl 3·3H2 O is 10:1-30:1 during loading of the active ingredient.
Preferably, during the loading of the active component, the concentration of the aqueous NaOH solution is 0.25-0.75 wt%, and the concentration of NaBH 4 is 1.0-2.0 mol/L.
Preferably, in the process of loading the active components, the dipping and dispersing time is 8-24 hours, the stirring and reducing time is 8-24 hours, the vacuum drying temperature is 50-120 ℃, and the drying time is 8-24 hours.
The method for synthesizing 2, 5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethylfurfural by using an iron-chromium bimetallic oxide catalyst loaded with ruthenium comprises the following specific steps:
Dissolving 5-hydroxymethylfurfural in deionized water, using oxygen as an oxygen source, using potassium bicarbonate as an additive, and using a ruthenium-loaded iron-chromium bimetallic oxide catalyst to catalyze the selective oxidation of 5-hydroxymethylfurfural to synthesize 2, 5-furandicarboxylic acid. The specific steps are as follows, and the following steps are sequentially carried out:
Oxidation of 5-hydroxymethylfurfural: adding 5-hydroxymethylfurfural, deionized water, ruthenium-loaded iron-chromium bimetallic oxide catalyst and KHCO 3 into a reaction kettle, introducing oxygen into the reaction kettle after the reaction kettle is installed, reacting under the condition of heating and stirring, stopping heating to reduce the temperature to room temperature, exhausting, and filtering out the catalyst. Diluting the reaction solution with purified water, and analyzing the diluted reaction solution by using a high performance liquid chromatograph, thereby calculating the conversion rate of 5-hydroxymethylfurfural and the yield of 2, 5-furandicarboxylic acid.
Purification of 2, 5-furandicarboxylic acid: collecting filtrate obtained after the reaction, removing water from the filtrate, adding concentrated hydrochloric acid until the pH is less than 1, crystallizing and separating 2, 5-furandicarboxylic acid from the filtrate, and obtaining white powdery 2, 5-furandicarboxylic acid through suction filtration, water washing and drying. The obtained white powdery product was dissolved in purified water and analyzed by high performance liquid chromatograph, thereby calculating the purity of 2, 5-furandicarboxylic acid.
Preferably, 0.2mmol of 5-hydroxymethylfurfural is dissolved in 5mL of deionized water, the reaction temperature is 80-120 ℃, the reaction time is 12-24 h, the oxygen pressure is 0.5-1.5 MPa, the dosage of the iron-chromium bimetallic oxide catalyst for supporting ruthenium is 0.05-0.15 g, and the dosage of KHCO 3 is 0-0.06 g.
Example 1:
the embodiment 1 of the invention discloses a preparation method of a ruthenium-supported chromium oxide catalyst, which comprises the following specific steps:
Preparing a precursor mixed solution: 6mmol Cr (NO 3)3·9H2 O is dissolved in 60mL deionized water, 1.5mol/L sodium hydroxide aqueous solution is dropwise added into the solution under the condition of intense stirring until PH is approximately equal to 10, and then the precursor chromium hydroxide mixed solution is obtained.
And (3) preparing a carrier: and (3) placing the precursor chromium hydroxide mixed solution in a hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 4 hours, cooling the hydrothermal treatment to room temperature, carrying out suction filtration, washing to neutrality, and drying at 60 ℃ for 12 hours to obtain precursor powder. Calcining the precursor powder at 400 ℃ for 4 hours in an air atmosphere, and cooling to room temperature to obtain the chromium oxide carrier, which is named Cr1-Fe0-O.
Loading active components: 0.0518g of RuCl 3·3H2 O (the load of ruthenium accounts for 4wt% of the carrier) was weighed and dissolved in 12.5mL of deionized water, 0.5g of the chromium oxide carrier was dispersed therein, and the mixture was immersed and dispersed in an ice-water bath under stirring for 12 hours. NaBH 4 is weighed according to the mol ratio of BH 4 -in NaBH 4 to Ru 3+ in RuCl 3·3H2 O of 20:1 and is dissolved in 0.5wt% NaOH aqueous solution, so that the concentration of NaBH 4 is 1.5mol/L. Then, the NaBH 4 aqueous solution containing NaOH is dropwise added into the dispersion liquid under the stirring condition of ice water bath, and stirring and reduction are continued for 12 hours. And (3) filtering, washing to be neutral, and vacuum drying at 60 ℃ for 12 hours to obtain the ruthenium-loaded chromium oxide catalyst which is named as 4wt% Ru/Cr1-Fe0-O.
In this example, the X-ray diffraction pattern of the chromium oxide support Cr1-Fe0-O is shown in FIG. 1, and it is understood from FIG. 1 that the characteristic diffraction peaks of Cr1-Fe0-O and Cr 2O3 are identical (JCPDS#04-0765).
Example 2:
The embodiment 2 of the invention discloses a preparation method of a ruthenium-supported iron-chromium bimetallic oxide catalyst, which comprises the following specific steps:
Preparing a precursor mixed solution: a total of 6mmol of Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O, in terms of Fe (NO 3)3·9H2 O to Cr (NO 3)3·9H2 O) molar ratio of 1:2, dissolved in 60mL of deionized water) was added dropwise to the above solution under vigorous stirring until the addition was stopped at pH of about 10, to give a precursor iron-chromium hydroxide mixture.
And (3) preparing a carrier: and (3) placing the precursor iron-chromium hydroxide mixed solution in a hydrothermal kettle for hydrothermal treatment at 180 ℃ for 4 hours, cooling the hydrothermal treatment to room temperature, filtering, washing to neutrality, and drying at 60 ℃ for 12 hours to obtain precursor powder. Calcining the precursor powder at 400 ℃ for 4 hours in an air atmosphere, and cooling to room temperature to obtain the Fe-Cr bimetallic oxide carrier named Cr2-Fe1-O.
Loading active components: 0.0518g RuCl 3·3H2 O (the load of ruthenium accounts for 4wt% of the carrier) was weighed and dissolved in 12.5mL deionized water, and 0.5g of the iron-chromium bimetallic oxide carrier was dispersed therein and placed in an ice-water bath to be immersed and dispersed for 12h under stirring. NaBH 4 is weighed according to the mol ratio of BH 4 -in NaBH 4 to Ru 3+ in RuCl 3·3H2 O of 20:1 and is dissolved in 0.5wt% NaOH aqueous solution, so that the concentration of NaBH 4 is 1.5mol/L. Then, the NaBH 4 aqueous solution containing NaOH is dropwise added into the dispersion liquid under the stirring condition of ice water bath, and stirring and reduction are continued for 12 hours. Filtering, washing to neutrality, and vacuum drying at 60 deg.c for 12 hr to obtain Fe-Cr bimetallic oxide catalyst with Ru load, named as 4wt% Ru/Cr2-Fe1-O.
In this example, the X-ray diffraction pattern of the Fe-Cr bimetallic oxide carrier Cr2-Fe1-O is shown in FIG. 1, and it can be seen from FIG. 1 that the diffraction peak of Cr2-Fe1-O is consistent with the characteristic diffraction peak of the corundum structure Cr 1.3Fe0.7O3 (JCPDS#35-1112), and is a Fe-Cr solid solution structure.
The X-ray photoelectron spectrum of the Ru/Cr2-Fe1-O catalyst loaded with 4wt% ruthenium prepared in this example is shown in FIG. 2, and it is clear from FIG. 2 that Ru, fe, cr, O elements are simultaneously present. The valence state of Fe can be observed in FIG. 2 (a), with peaks at 2p 3/2 and 2p 1/2 at about 709.82eV and 723.72eV, respectively. The spin-orbit splitting energy between the two peaks was about 13.9eV, confirming the coexistence of Fe 2+ and Fe 3+. In addition, satellite peaks were also introduced to obtain a best fit. The fitted peaks with binding energies 710.04eV and 723.30eV correspond to the characteristic peaks of Fe 2+ at the orbits of Fe2P 3/2 and Fe2P 1/2, respectively, and the fitted peaks with binding energies 712.72eV and 726.03eV correspond to the characteristic peaks of Fe 3+ at the orbits of Fe2P 3/2 and Fe2P 1/2, respectively. The satellite peaks for Fe 2+ at Fe2p 1/2 and Fe2p 3/2 at 716.43eV and 728.96eV, respectively, and the satellite peaks for Fe 3+ at Fe2p 1/2 and Fe2p 3/2 at 719.51eV and 732.96eV, respectively. FIG. 2 (b) is an XPS plot of the Cr 2p 3/2 orbits, which can be fit to three peaks, peaks with binding energies 576.08eV and 577.19eV corresponding to Cr 3+ and binding energies 578.34 corresponding to Cr 6+. FIG. 2 (c) shows an XPS spectrum of O1s, wherein the O1s is divided into three peaks respectively located at 529.69eV, 531.01eV and 532.53eV, and the three peaks belong to three types of peaks of lattice oxygen, oxygen defects or water molecules adsorbed by the surface of the oxygen. FIG. 2 (d) shows two peaks of Ru 3p orbitals, at 461.86eV and 464.48eV, respectively, corresponding to Ru 0 and Ru 4+, due to the oxidation of part of the metallic Ru 0 species to the higher-valence Ru 4+ species by exposure of the catalyst to air.
As can be seen from the EDS spectrum of the Ru/Cr2-Fe1-O catalyst loaded with 4wt% of ruthenium prepared in the embodiment shown in FIG. 3, the mass of Ru is 3.991wt%, and the Cr/Fe molar ratio in Fe1-Cr2-O is about 2.01 and is close to the theoretical value.
Example 3:
the embodiment 3 of the invention discloses a preparation method of a ruthenium-supported iron-chromium bimetallic oxide catalyst, which comprises the following specific steps:
Preparing a precursor mixed solution: a total of 6mmol of Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O, in terms of Fe (NO 3)3·9H2 O to Cr (NO 3)3·9H2 O) molar ratio of 2:1, dissolved in 60mL of deionized water) was added dropwise to the above solution under vigorous stirring until the dropwise addition was stopped at pH of about 10, to give a precursor iron-chromium hydroxide mixture.
And (3) preparing a carrier: and (3) placing the precursor iron-chromium hydroxide mixed solution in a hydrothermal kettle for hydrothermal treatment at 180 ℃ for 4 hours, cooling the hydrothermal treatment to room temperature, filtering, washing to neutrality, and drying at 60 ℃ for 12 hours to obtain precursor powder. Calcining the precursor powder at 400 ℃ for 4 hours in an air atmosphere, and cooling to room temperature to obtain the Fe-Cr bimetallic oxide carrier named Cr1-Fe2-O.
Loading active components: 0.0518g RuCl 3·3H2 O (the load of ruthenium accounts for 4wt% of the carrier) was weighed and dissolved in 12.5mL deionized water, and 0.5g of the iron-chromium bimetallic oxide carrier was dispersed therein and placed in an ice-water bath to be immersed and dispersed for 12h under stirring. NaBH 4 is weighed according to the mol ratio of BH 4 -in NaBH 4 to Ru 3+ in RuCl 3·3H2 O of 20:1 and is dissolved in 0.5wt% NaOH aqueous solution, so that the concentration of NaBH 4 is 1.5mol/L. Then, the NaBH 4 aqueous solution containing NaOH is dropwise added into the dispersion liquid under the stirring condition of ice water bath, and stirring and reduction are continued for 12 hours. Filtering, washing to neutrality, and vacuum drying at 60 deg.c for 12 hr to obtain Fe-Cr bimetallic oxide catalyst with Ru load, named as 4wt% Ru/Cr1-Fe2-O.
In this example, the X-ray diffraction pattern of the Fe-Cr bimetallic oxide carrier Cr1-Fe2-O is shown in FIG. 1, and it is known from FIG. 1 that the diffraction peak of Cr1-Fe2-O is similar to the characteristic diffraction peak of Cr 1.3Fe0.7O3 in corundum structure (JCPDS#35-1112). Cr1-Fe2-O is a Fe-Cr solid solution structure and may contain a small amount of Fe 2O3.
Example 4:
the embodiment 4 of the invention discloses a preparation method of a ruthenium-loaded iron oxide catalyst, which comprises the following specific steps:
Preparing a precursor mixed solution: 6mmol of Fe (NO 3)3·9H2 O is dissolved in 60mL of deionized water, 1.5mol/L sodium hydroxide aqueous solution is dropwise added into the solution under the condition of intense stirring until the PH is approximately equal to 10, and the precursor ferric hydroxide mixed solution is obtained.
And (3) preparing a carrier: and (3) placing the precursor ferric hydroxide mixed solution in a hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 4 hours, cooling the hydrothermal treatment to room temperature, carrying out suction filtration, washing to neutrality, and drying at 60 ℃ for 12 hours to obtain precursor powder. Calcining the precursor powder at 400 ℃ for 4 hours in an air atmosphere, and cooling to room temperature to obtain the ferric oxide carrier, which is named as Cr0-Fe1-O.
Loading active components: 0.0518g of RuCl 3·3H2 O (the load of ruthenium is 4wt% of the carrier) was weighed and dissolved in 12.5mL of deionized water, 0.5g of the iron oxide carrier was dispersed therein, and the solution was immersed and dispersed in an ice-water bath under stirring for 12 hours. NaBH 4 is weighed according to the mol ratio of BH 4 -in NaBH 4 to Ru 3+ in RuCl 3·3H2 O of 20:1 and is dissolved in 0.5wt% NaOH aqueous solution, so that the concentration of NaBH 4 is 1.5mol/L. Then, the NaBH 4 aqueous solution containing NaOH is dropwise added into the dispersion liquid under the stirring condition of ice water bath, and stirring and reduction are continued for 12 hours. Filtering, washing to neutrality, and vacuum drying at 60 deg.c for 12 hr to obtain the supported Ru-Fe oxide catalyst named 4wt% Ru/Cr0-Fe1-O.
In this example, the X-ray diffraction pattern of the siderophore Cr0-Fe1-O is shown in FIG. 1, and it is understood from FIG. 1 that the characteristic diffraction peaks of Cr0-Fe1-O and Fe 2O3 are identical (JCPDS#06-0502).
Example 5:
The catalyst is used for catalyzing 5-hydroxymethylfurfural to synthesize 2, 5-furandicarboxylic acid, and the specific steps are as follows:
Oxidation of 5-hydroxymethylfurfural: adding 0.2mmol of 5-hydroxymethylfurfural, 0.06g of KHCO 3, 5mL of deionized water and 0.1g of catalyst into a reaction kettle, introducing 1.0MPa of oxygen into the reaction kettle after the reaction kettle is installed, reacting for 16h under the stirring condition at 100 ℃, stopping heating to cool the temperature to room temperature, exhausting, and filtering out the catalyst. Diluting the reaction solution with purified water, and analyzing the diluted reaction solution by using a high performance liquid chromatograph, thereby calculating the conversion rate of 5-hydroxymethylfurfural and the yield of 2, 5-furandicarboxylic acid.
Purification of 2, 5-furandicarboxylic acid: collecting filtrate obtained after the reaction, removing water from the filtrate, adding concentrated hydrochloric acid until the pH is less than 1, crystallizing and separating 2, 5-furandicarboxylic acid from the filtrate, and obtaining white powdery 2, 5-furandicarboxylic acid through suction filtration, water washing and drying. The obtained white powdery product was dissolved in purified water and analyzed by high performance liquid chromatograph, thereby calculating the purity of 2, 5-furandicarboxylic acid.
Liquid phase test conditions: UV detector, C18 column (250 mm. Times.4.6 mm,5 μm), 0.1wt% aqueous formic acid: water=3:7 was used as mobile phase, column temperature 25 ℃, sample injection amount 5 μl, peak position and peak area were recorded, and quantitative analysis was performed by external standard method.
Example 6, example 7, example 8, example 9, example 10:
The reaction was carried out using only Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O in different molar ratios) with NO Ru loading under the same reaction conditions as in example 5, and the reaction results are shown in table 1 below.
TABLE 1 catalytic results for supports of different Fe/Cr molar ratios
Note that: 5-Hydroxymethylfurfural (HMF), 2, 5-furandicarboxylic acid (FDCA), 5-hydroxymethyl-2-furancarboxylic acid (HFCA), 5-formyl-2-furancarboxylic acid (FFCA).
Table 1 shows the catalytic results of the carriers with different Fe/Cr molar ratios, and the HMF conversion rate is improved after the carriers are added as catalysts compared with the carriers without the catalysts, so that the carriers have certain catalytic activity. Wherein the catalytic effect of Cr2-Fe1-O as a carrier is optimal, the HMF conversion rate is 75.8%, and the FDCA yield is 13.0%.
Example 11, example 12, example 13, example 14:
The reaction was carried out under the same reaction conditions as in example 5, using Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O in different molar ratios) with 4wt% Ru as a catalyst, and the reaction results are shown in Table 2 below.
TABLE 2 catalytic results of 4wt% Ru catalyst on supports with different Fe/Cr molar ratios
Table 2 shows the catalytic results of supported Ru catalysts with different Fe/Cr molar ratios. As can be seen from comparison of Table 1, the catalytic activity of the supported ruthenium catalyst was significantly improved. Fe (NO 3)3·9H2 O and Cr (when the mol ratio of NO 3)3·9H2 O is 1:2), the catalytic performance is optimal, the conversion rate of the raw material HMF is 100%, the yield of the target product FDCA is 99.9%, and byproducts HFCA and FFCA are not generated.
Example 12, example 15, example 16:
The reaction was carried out under the same reaction conditions as in example 5 with different loadings of ruthenium on the Cr2-Fe1-O carrier, and the reaction results are shown in Table 3 below.
TABLE 3 influence of ruthenium loading on catalytic Properties
As can be seen from table 3, the catalytic activity increased with increasing ruthenium loading. When the loading is 2wt%, the HMF can be completely converted, the yield of FDCA is 85.8%, when the loading is increased to 3wt%, the yield of FDCA is improved to 96.0%, and when the loading is increased to 4wt%, the catalytic effect is optimal, and the yield of FDCA reaches 99.9%.
Example 12, example 17, example 18, example 19:
The reaction was catalyzed by 4wt% Ru/Cr2-Fe1-O catalyst under the same reaction conditions as in example 5, and the reaction results are shown in Table 4 below when the amount of KHCO 3 used was varied.
TABLE 4 influence of KHCO 3 amount on catalytic Properties
From Table 4, it is clear that the amount of KHCO 3 used has a significant effect on the catalytic effect. Without the addition of KHCO 3, HMF was not completely converted, and the yield of FDCA was only 6.6%. The HMF was completely converted by adding 0.02g KHCO 3, and the yield of FDCA was increased to 30.3%. 0.04g KHCO 3 was added and the yield of FDCA increased to 54.0%. When KHCO 3 was used in an amount of 0.06g, the yield of FDCA could reach 99.9%.
Example 12, example 20, example 21, example 22, example 23:
The reaction was catalyzed by 4wt% Ru/Cr2-Fe1-O catalyst under the same reaction conditions as in example 5, and the reaction was carried out at different reaction temperatures, the reaction results being shown in Table 5 below.
TABLE 5 influence of the reaction temperature on the catalytic properties
As can be seen from Table 5, the HMF conversion was complete at a reaction temperature of 80-120℃and the FDCA yield tended to increase and decrease with increasing temperature, with the highest FDCA yield reaching 99.9% at 100 ℃.
Example 12, example 24, example 25, example 26:
the reaction was catalyzed by 4wt% Ru/Cr2-Fe1-O catalyst under the same reaction conditions as in example 5, and was carried out at various reaction times, the reaction results being shown in Table 6 below.
TABLE 6 influence of reaction time on catalytic properties
As can be seen from Table 6, at a reaction time of 12h, the HMF was completely converted, the yield of FDCA was 97.0%, and the yields of by-products HFCA and FFCA were 0.5% and 2.5%, respectively. The reaction time was prolonged to 16h, the yield of FDCA was 99.9%, and HFCA and FFCA were not present. Continuing to increase the reaction time, the yield of FDCA decreased, and at 20h of reaction, the yield of FDCA was 89.1%. The yield of FDCA was 62.7% at 24h of reaction.
Example 12, example 27, example 28:
the reaction was catalyzed by 4wt% Ru/Cr2-Fe1-O catalyst under different oxygen pressures under the same reaction conditions as in example 5, and the reaction results are shown in Table 7 below.
TABLE 7 influence of oxygen pressure on catalytic performance
From Table 7, it is understood that the conversion of HMF was 99.7% and the yield of FDCA was only 10.8% with HFCA and FFCA yields of 6.4% and 6.9%, respectively, when the oxygen pressure was 0 MPa. As the oxygen pressure increased to 0.5MPa, the HMF was able to achieve full conversion, the FDCA yield increased to 64.6%, and HFCA and FFCA yields decreased to 1.5% and 3.0%, respectively. At an oxygen pressure of 1.0MPa, 100% HMF conversion and 99.9% FDCA yield can be obtained.
Example 12, example 29, example 30, example 31:
The reaction was catalyzed by 4wt% Ru/Cr2-Fe1-O catalyst under the same reaction conditions as in example 5, and the reaction results are shown in Table 8 below when the catalyst amounts were varied.
TABLE 8 influence of catalyst usage on catalytic Properties
It can be seen from Table 8 that without the addition of catalyst, 69.6% HMF conversion and 18.4% FDCA yield were obtained with yields of intermediate HFCA and FFCA of 6.7% and 4.8%, respectively. When 0.05g of catalyst was added to the reaction system, the HMF was able to be converted completely, and yields of FDCA, HFCA and FFCA were obtained at 95.4% and 0.6% and 3.9%, respectively. As the catalyst usage continued to increase to 0.1g, the FDCA yield increased to 99.9%. Continuing to increase the catalyst usage to 0.15g, the HMF was fully converted, but the FDCA yield was reduced to 55.9%, and the HFCA and FFCA yields were 0.5% and 2.5%, respectively.
Claims (7)
1. The preparation method of the ruthenium-loaded iron-chromium bimetallic oxide catalyst for synthesizing 2, 5-furandicarboxylic acid by using 5-hydroxymethylfurfural is characterized by comprising the following steps of: comprising the following steps, and the following steps are carried out in sequence,
Step one, preparing a precursor mixed solution:
Dissolving Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O in deionized water according to a selected molar ratio, and dropwise adding a sodium hydroxide aqueous solution into the solution under the condition of stirring rotation speed of 500 rpm until the PH is 9-11, and stopping dropwise adding to obtain a precursor ferrochrome hydroxide mixed solution;
Step two, preparing a carrier:
placing the precursor iron-chromium hydroxide mixed solution in a hydrothermal kettle for hydrothermal treatment, after the hydrothermal treatment is finished and cooled to room temperature, filtering and washing the precipitate to be neutral, drying to obtain precursor powder, calcining the precursor powder in an air atmosphere, and cooling to room temperature to obtain an iron-chromium bimetallic oxide carrier;
Step three, loading active components:
Weighing deionized water, dissolving RuCl 3·3H2 O in the deionized water, weighing an iron-chromium bimetallic oxide carrier, dispersing the carrier in the deionized water, then soaking and dispersing in an ice water bath under a stirring state to obtain a dispersion liquid, dropwise adding an aqueous solution of NaBH 4 containing NaOH into the dispersion liquid under the stirring condition of the ice water bath, continuously stirring and reducing, filtering and washing a precipitate to be neutral, and vacuum drying to obtain the ruthenium-loaded iron-chromium bimetallic oxide catalyst;
in the first step, fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O are in a molar ratio of 1:2).
2. The preparation method according to claim 1, characterized in that: in the first step, fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O are dissolved in deionized water) is specifically selected from the group consisting of Fe (NO 3)3·9H2 O and Cr (NO 3)3·9H2 O are dissolved in 60mL deionized water in total at 6 mmol; and the concentration of the aqueous sodium hydroxide solution is 1.0 mol/L-2.0 mol/L).
3. The preparation method according to claim 1, characterized in that: the specific conditions of the hydrothermal process in the second step are as follows: the hydrothermal temperature is 160-200 ℃, and the hydrothermal time is 3 h-6 h;
The specific conditions for calcination are: the calcination temperature is 350-500 ℃ and the calcination time is 2-6 h;
the specific conditions for drying are as follows: the drying temperature is 50-120 ℃, and the drying time is 8 h-24 h.
4. The preparation method according to claim 1, characterized in that: and in the third step, the deionized water is weighed to be 12.5 mL, the weighed iron-chromium bimetallic oxide carrier is 0.5 g, the addition amount of RuCl 3·3H2 O is 0.0259 g~0.0518 g, and the load amount of ruthenium accounts for 2 wt% -4 wt% of the carrier.
5. The preparation method according to claim 1, characterized in that: the concentration of the NaOH aqueous solution in the third step is 0.25 wt% -0.75 wt%, the concentration of NaBH 4 is 1.0 mol/L-2.0 mol/L, and the molar ratio of BH 4 -in NaBH 4 to Ru 3+ in RuCl 3·3H2 O is 10:1-30:1.
6. The preparation method according to claim 1, characterized in that: in the third step, the dipping and dispersing time is 8 h-24: 24 h, the stirring and reducing time is 8 h-24: 24 h, the drying temperature of vacuum drying is 50-120 ℃, and the drying time is 8 h-24: 24 h.
7. The method for synthesizing 2, 5-furandicarboxylic acid by using the ruthenium-loaded iron-chromium bimetallic oxide catalyst, which is prepared by the preparation method of claim 1, is characterized in that: comprising the following steps, and the following steps are carried out in sequence,
Step one, oxidizing 5-hydroxymethylfurfural:
Adding 5-hydroxymethylfurfural, deionized water, ruthenium-loaded iron-chromium bimetallic oxide catalyst and KHCO 3 into a reaction kettle, introducing oxygen into the reaction kettle after the reaction kettle is installed, reacting under the condition of heating and stirring, stopping heating to reduce the temperature to room temperature, exhausting gas, filtering out the catalyst, diluting the reaction liquid with purified water, and analyzing the diluted reaction liquid by using a high performance liquid chromatograph, thereby calculating the conversion rate of 5-hydroxymethylfurfural and the yield of 2, 5-furandicarboxylic acid;
step two, purifying 2, 5-furandicarboxylic acid:
Collecting filtrate obtained after the reaction, removing water from the filtrate, adding concentrated hydrochloric acid until the pH is less than 1, crystallizing and separating 2, 5-furandicarboxylic acid from the filtrate, filtering, washing with water, drying to obtain white powdery 2, 5-furandicarboxylic acid, dissolving the obtained white powdery product in purified water, and analyzing by using a high performance liquid chromatograph to calculate the purity of the 2, 5-furandicarboxylic acid;
The usage amount of the 5-hydroxymethylfurfural, deionized water, ruthenium-loaded iron-chromium bimetallic oxide catalyst and KHCO 3 and the reaction conditions are as follows:
0.2 mmol of 5-hydroxymethylfurfural is dissolved in 5 mL deionized water, the reaction temperature is 80-120 ℃, the reaction time is 12 h-24 h, the oxygen pressure is 0.5-MPa-1.5 MPa, the dosage of the iron-chromium bimetallic oxide catalyst loaded with ruthenium is 0.05-g-0.15 g, and the dosage of KHCO 3 is 0.02-0.06 g.
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