CN111135828B - Catalyst and application, preparation and performance test method of catalyst - Google Patents
Catalyst and application, preparation and performance test method of catalyst Download PDFInfo
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- CN111135828B CN111135828B CN202010002928.9A CN202010002928A CN111135828B CN 111135828 B CN111135828 B CN 111135828B CN 202010002928 A CN202010002928 A CN 202010002928A CN 111135828 B CN111135828 B CN 111135828B
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Abstract
The invention relates to a catalyst, and an application, preparation and performance test method of the catalyst, wherein the catalyst is a tin-manganese composite oxide loaded nano platinum catalyst, in particular to a Pt/Sn catalyst x Mn 1 O y A catalyst. The application method of the catalyst is to prepare gamma-valerolactone by catalytically hydrogenating levulinic acid. Pt/Sn prepared by the invention x Mn 1 O y The catalyst has novel chemical composition, is easy to separate and recover, and the yield of the gamma-valerolactone is kept above 99 percent when the cycle times in the repeated use process is 3 times.
Description
Technical Field
The invention relates to a preparation method of a catalyst and the application field thereof, in particular to an unreported preparation method of a tin-manganese composite oxide supported nano platinum catalyst and the application thereof in hydrogenolysis (hydrogenation hydrolysis) reaction.
Background
The large-scale utilization of fossil energy has greatly promoted the development of human society and economy, but also has brought about inevitable derivative problems of global warming, air pollution and energy shortage. In recent years, in order to alleviate the increasingly serious problems of environmental pollution and global energy crisis, researchers are gradually seeking to develop new green renewable resource utilization schemes. The wood biomass resource is a natural clean renewable energy source with wide source, abundant reserves and low price, and has the potential of being converted into various important liquid fuels and high value-added chemicals and the potential of being used for replacing the traditional fossil energy greatly. Among these, the synthesis of gamma valerolactone, which is considered to be the most promising biomass-derived platform molecule, is one of the key steps in the conversion of biomass resources into liquid fuels and high value-added chemicals. Gamma valerolactone has attractive physicochemical properties and potential fuel applications, is non-toxic and biodegradable; can be used as food additive and fuel additive, green solvent and nylon intermediate, and can be further upgraded and converted into various derivatives such as methyl tetrahydrofuran, alkane and 1, 4-pentanediol. At present, the key point of scientific research is the optimization of the production process for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid, which is a biomass platform molecule.
At present, the developed catalysts for catalyzing levulinic acid hydrogenation to produce gamma-valerolactone are mainly divided into: homogeneous catalysts and heterogeneous catalysts. Homogeneous catalysts require complex synthetic steps and are expensive, have poor durability and are difficult to recycle, which greatly limits their large scale application in industrial catalysis. The gas phase hydrogenation process with heterogeneous catalyst has energy sensitivity to the vaporization of levulinic acid (the boiling point of levulinic acid is 245-246 ℃), the required working temperature is very high, and the requirements on production equipment are very strict. In contrast, liquid phase hydrogenation processes are simple and more economical and have attracted the attention of researchers. However, the non-noble metal catalyst used in industry, such as Cu-based catalyst, has low catalyst activity, low target yield, working temperature generally above 200 ℃, working pressure above 30 atmospheres (3 MPa), poor catalyst repeatability, easy loss of active metal, and easy generation of high yield coke. In the case of a noble metal catalyst used industrially, such as Ru/C, which operates at a temperature of 150 ℃ or higher and at a pressure of 30 atmospheres or higher, the active noble metal component is rapidly deactivated during the reaction and the deactivation is irreversible, which leads to a great increase in production cost.
Therefore, in order to take the production cost of the catalyst into consideration, the simplification of production equipment and the high yield of the target product gamma-valerolactone into consideration; at present, a heterogeneous catalyst which is designed to efficiently catalyze levulinic acid to produce gamma-valerolactone through liquid-phase hydrogenation under the conditions of low temperature and low pressure and has strong stability is very needed.
The prior art has the following defects:
1) The homogeneous catalyst used in the process of preparing gamma-valerolactone by hydrogenating levulinic acid in industry has complex preparation process, expensive ligand, poor catalyst recycling effect and difficult recovery.
2) The gas phase hydrogenation requires high energy input to vaporize the levulinic acid to participate in the reaction, the used reaction equipment is expensive, the reaction conditions are harsh, the reaction risk coefficient is large, and further the production cost is increased.
3) Although the commonly used noble metal catalysts of Ir, ru, pd, pt and the like have good catalytic performance and recycling availability, the loading amount is generally higher, so that the production cost is greatly increased. In addition, the use of chemical additives limits their use in industry.
4) The industrial non-noble metal catalyst contains metal elements such as Ni, cr and the like, and has the defects of carcinogenicity, serious water pollution caused by discharge of reaction waste liquid, large catalyst consumption, difficult acquisition of high catalytic activity and low economic benefit. In particular, the active metal is easily lost during the catalytic reaction, and a large amount of coke is easily generated, which undoubtedly increases the technological process of separation and purification.
5) Although platinum-based noble metal catalysts have good activity and selectivity, there is a problem that the reaction conditions of the catalysts are severe, such as the use of V in the study of K.Kaneda in Green chem, 2015, 17, 5136-5139 in 2015 2 O 5 Pt-supported catalyst at 130 ℃,5MPa H 2 And 6h, the conversion rate of high-concentration levulinic acid is completely converted>99 percent of the selectivity, high hydrogen pressure and high carrier toxicity; 2018 Nicole Wilde in front. Chem.,2018,6, 143, using a Y-type zeolite supported Pt catalyst at 220 ℃ and 2.5MPa H 2 Under the condition of (1), levulinic acid is completely converted within 24h, and the selectivity to gamma-valerolactone is only 92 percent, which has the problems of very high reaction temperature and low yield.
6) The performance of the supported nano platinum catalyst greatly depends on the selection of the carrier, and some carriers cannot realize high dispersion of the noble metal nano particles and cannot prevent the noble metal from sintering and aggregating in the use process of the catalyst.
Disclosure of Invention
The invention aims to solve the defects of the problems and provides a catalyst and an application, preparation and performance test method of the catalyst. The invention is intended to achieve the following technical objects: 1) A heterogeneous catalyst which is simple in preparation method, novel in chemical composition, easy to separate and recover and high in reusability is developed. 2) The catalyst is nontoxic and harmless, has no loss of active metal and no generation of byproducts and coke in the production process of preparing the gamma-valerolactone by hydrogenating the levulinic acid, and meets the low-carbon and green chemical concepts. 3) The supported nano noble metal catalyst is prepared by using Pt with excellent hydrogenation performance, but Pt with high loading or other additives is not used to reduce the cost. 4) A cheap metal composite oxide is developed to load noble metal Pt, so that the high dispersion of noble metal nano particles is realized. 5) By optimizing the preparation method of the catalyst, the activity, the selectivity and the yield of the target product of the catalyst are improved. 6) Reaction conditions are optimized, so that the catalyst can completely convert high-concentration levulinic acid under the working conditions of less than 150 ℃ and less than 3MPa, the selectivity is more than 99%, the requirements on reaction equipment and the operation risk coefficient are reduced, and the production economic benefit is improved. 7) A tin-manganese composite oxide supported nano platinum catalyst is developed, and the most important is to adjust the proportion of a tin-manganese carrier and the pre-reduction mode of a noble metal Pt.
The invention is realized by adopting the following technical scheme.
The catalyst of the invention is a tin-manganese composite oxide loaded nano platinum catalyst, in particular to Pt/Sn x Mn 1 O y A catalyst.
Further, the invention relates to Pt/Sn x Mn 1 O y The catalyst is Pt/Sn 0.8 Mn 1 O y A catalyst.
Further, the Pt/Sn of the invention 0.8 Mn 1 O y The catalyst is reduced by sodium borohydride.
The application method of the catalyst is to prepare the gamma-valerolactone by catalytically hydrogenating the levulinic acid.
The preparation method of the catalyst comprises the following steps:
s1, snCl 2 ·2H 2 O and Mn (NO) 3 ) 2 ·4H 2 Dissolving O in methanol, and stirring to obtain a uniform solution;
s2, adding triethylamine into the uniform solution in the S1, uniformly precipitating, adding deionized water, and then controlling the temperature of the suspension and carrying out aging treatment;
s3, carrying out suction filtration on the aged suspension, washing to obtain a neutral filter cake, and then drying;
s4, grinding the filter cake in the S3, roasting, and cooling to room temperature to obtain Sn x Mn 1 O y A carrier;
s5, dropwise adding hexachloroplatinic acid solution into the polyvinylpyrrolidone aqueous solution under the condition of keeping out of the sun, and violently stirring;
s6, sn prepared in S4 x Mn 1 O y Adding a carrier into the mixed solution in the S5, immediately dropwise adding a sodium borohydride solution, stirring after dropwise adding, carrying out suction filtration and washing on the solution, and placing a filter cake at a high temperature; taking out the solid powder, and storing under the dark drying condition to obtain Pt/Sn x Mn 1 O y A catalyst.
Further, in the step S1, snCl is adopted 2 ·2H 2 O and Mn (NO) 3 ) 2 ·4H 2 When O was dissolved in methanol, the mixture was stirred by a magnetic stirrer, and the rotation speed of the magnetic stirrer was 550rpm.
Further, in the step S2, triethylamine is added dropwise to the homogeneous solution in the step S1 until the solution pH =9, 50-75ml of deionized water is added, the temperature of the suspension is controlled at 55-75 ℃, and the suspension is aged for at least 12 hours.
Further, in the S3, the aged suspension is poured into a sand core funnel, is subjected to suction filtration, is washed by deionized water until the pH of the solution is =7, and after washing is finished, a filter cake is dried for 8-14 hours at the temperature of 100-120 ℃;
further, in the S4, the filter cake in the S4 is ground into powder and then is roasted for 4 hours at 400 ℃ in a muffle furnace, wherein the temperature rise rate is 2 ℃/min.
Further, in S5, 6-12mg of polyvinylpyrrolidone is prepared into an aqueous solution and added into 150ml of water, 1.00-2.00ml of hexachloroplatinic acid solution with the concentration of 4.76mg/ml is transferred and added, and the mixture is stirred by a magnetic stirrer, wherein the rotating speed of the magnetic stirrer is 550rpm.
Further, in the S6, 1-2L of deionized water with the temperature of 70-90 ℃ is used for washing a filter cake during suction filtration, and after washing is finished, the obtained filter cake is placed at the temperature of 70-90 ℃ for 10-14h.
The performance test method of the catalyst comprises the following steps:
step one, sequentially adding the tin-manganese composite oxide load nano platinum catalyst prepared in the step 6, magnetons, levulinic acid and dioxane into a polytetrafluoroethylene lining of an intermittent high-pressure reaction kettle;
step two, after the reaction kettle is installed, purging with argon for three times, extracting vacuum, connecting the reaction kettle with a hydrogen steel cylinder, introducing hydrogen for purging for three times, and raising the pressure of the hydrogen to keep the pressure in the kettle at 1.6-2.4MPa;
step three, putting the reaction kettle into an oil bath kettle with a preset stable temperature, and simultaneously starting magnetic stirring;
and step four, starting timing when the temperature in the kettle reaches 120 ℃, taking out the reaction kettle after the reaction lasts for 4-8 hours, releasing gas in the kettle after cooling by using an ice water bath, sucking reaction liquid in the kettle by using an injector, filtering by using a micron filter head, diluting the filtrate, and then carrying out quantitative analysis by using a gas chromatograph.
Further, the performance test method of the invention comprises the following parameters: hydrogen pressure: 2MPa; reaction temperature: 120 ℃; reaction time: 6h; solvent: 10ml of dioxane.
The invention has the beneficial effects that 1, the tin-manganese composite oxide load nano platinum catalyst prepared by the invention is Pt/Sn x Mn 1 O y The catalyst has novel chemical composition, is easy to separate and recover, and when the cycle number is 3 times in the repeated use process, the yield of the gamma-valerolactone is also kept above 99 percent.
2. Compared with non-noble metal catalysts, the catalyst prepared by the method has no toxicity, the catalyst dosage in the production process is small, no active metal loss exists, and no by-product or coke is generated.
3. Compared with the precious metal catalysts such as Ir, ru, pd and the like reported in the literature, the precious metal loading capacity of the catalyst prepared by the method is very low (2 wt.%) and no chemical additive is used in the reaction process.
4. Compared with other catalysts, the catalyst prepared by the invention uses cheap and easily-obtained tin and manganese non-noble metals as carriers, realizes high dispersion (average particle size is 2.8 nm) of noble metal nanoparticles, has uniform particle size distribution, and effectively prevents sintering and aggregation of noble metals.
5. The invention optimizes the preparation method of the catalyst, successfully adjusts the proportion of the tin-manganese carrier and takes sodium borohydride reduction as the best pre-reduction mode of the noble metal Pt.
6. The optimized reaction conditions (hydrogen pressure: 2MPa, reaction temperature: 120 ℃, reaction time: 6h, solvent: 10ml dioxane) of the invention realize the optimal catalytic effect under the mild conditions, completely convert high-concentration levulinic acid, and have the selectivity of more than 99%.
The invention is further explained below with reference to the drawings and the detailed description.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) spectrum of carriers with different tin-manganese ratios under roasting at 400 ℃.
Wherein: (a) Mn (Mn) 3 O 4 ；(b)Sn 0.5 Mn 1 O y ，(c)Sn 0.8 Mn 1 O y ；(d)Sn 2 Mn 1 O y ；(e)SnO x 。
FIG. 2.2wt.% Pt/Sn 0.8 Mn 1 O y Transmission Electron Microscopy (TEM) characterization of the catalyst and the corresponding Pt nanoparticle size distribution plot.
FIG. 3 shows Pt/Sn according to the present invention 0.8 Mn 1 O y A reaction path diagram of the catalyst for catalyzing levulinic acid hydrogenation to prepare gamma-valerolactone.
Detailed Description
As can be seen from FIG. 1, for Mn 3 O 4 Sample, a series of diffraction peaks, attributed to Mn, occurred at 2 θ =18.0 °,28.9 °,31.0 °,32.3 °,36.1 ° and 59.8 ° 3 O 4 Characteristic diffraction peaks of the phases (PDF # 24-0734). For SnO x Sample, two phases are present: a series of diffraction peaks appearing at 2 θ =29.9 °,33.3 °,50.7 °,57.4 °,62.1 ° and 62.5 °, which are characteristic diffraction peaks (PDF # 06-0395) attributed to tetragonal SnO phase (cassiterite); the diffraction peaks appearing at 2 θ =26.6 °,33.9 °,37.9 °,51.8 °,54.8 °,64.7 °,65.9 ° and 78.7 ° are assigned to tetragonal rutile SnO 2 Characteristic diffraction peaks of the phases (PDF # 41-1445). The XRD diffraction peaks of the tin-manganese composite oxide were also characterized by those of the above-mentioned single oxides, and the above results indicate that the tin-manganese composite oxide is composed of trimanganese tetraoxide, stannous oxide and stannic oxide.
As can be seen from the characterization of the transmission electron microscope of FIG. 2, sn 0.8 Mn 1 O y The average particle size of the Pt nanoparticles loaded on the carrier is 2.8nm, the particle size distribution accords with normal distribution, and the phenomenon of Pt nanoparticle aggregation is not observed. The optimized preparation method of the catalyst provided by the invention realizes high dispersion of Pt nanoparticles by taking sodium borohydride reduction as an optimal pre-reduction mode of noble metal Pt.
The tin-manganese composite oxide load platinum catalyst prepared by the invention is Pt/Sn 0.8 Mn 1 O y Catalyst, using the reaction path of fig. 3: under the action of Pt nanoparticles, hydrogen molecules are split into hydrogen atoms and added to the carbonyl group of levulinic acid resulting in the formation of 4-hydroxyvaleric acid, a reaction intermediate. Then at Sn 0.8 Mn 1 O y Under the action of acid sites of the carrier, 4-hydroxypentanoic acid is rapidly dehydrated and closed-loop-closed to generate gamma-valerolactone, and particularly, strong interaction may exist between noble metal platinum and a metal carrier tin element. Therefore, the catalyst prepared by the invention can completely convert high-concentration levulinic acid and has excellent gamma-valerolactone selectivity.
The following describes in detail an implementation of the present invention, but the scope of the present invention is not limited to the following.
Example 1:
the preparation method of the tin-manganese composite oxide supported platinum catalyst with different proportions comprises the following steps:
s1, on a magnetic stirrer with the rotating speed of 550rpm, 1.81g of SnCl with the mass molar concentration of 4.42mmol/g 2 ·2H 2 O and 2.51g Mn (NO) with a molarity of 3.98mmol/g 3 ) 2 ·4H 2 Dissolving O in 100ml of methanol, and stirring to obtain a uniform solution;
s2, dropwise adding triethylamine into the uniform solution in the S1 to uniformly precipitate until the pH of the solution is =9, then adding 50ml of deionized water, controlling the temperature of the suspension at 65 ℃ and carrying out aging treatment for 18 hours;
s3, pouring the aged suspension into a sand core funnel, performing suction filtration, washing with deionized water until the pH of the filter cake is =7, and drying the obtained filter cake at 110 ℃ overnight;
s4, grinding the filter cake in the S3 into powder, roasting for 4 hours at 400 ℃ in a muffle furnace at the heating rate of 2 ℃/min, taking out after cooling to room temperature to prepare Sn 0.8 Mn 1 O y A carrier; according to SnCl 2 ·2H 2 O and Mn (NO) 3 ) 2 ·4H 2 The molar amount of O added was different, i.e. different Sn/Mn molar ratio (Sn/Mn =2,1,0.8,0.5,0.25), giving Sn x Mn 1 O y A carrier;
s5, under the condition of keeping out of the sun and under the magnetic stirring condition with the rotation speed of 550rpm, weighing 6mg of polyvinylpyrrolidone, dissolving in 0.6ml of water, adding into 150ml of water, and then transferring 1.00ml of hexachloroplatinic acid solution with the concentration of 4.76mg/ml for rapid addition; stirring for 15min;
s6, weighing Sn prepared in 238mg S4 x Mn 1 O y Adding a carrier into the mixed solution in the S5, then weighing 20mg of sodium borohydride, dissolving the sodium borohydride in 4.8ml of water, dropwise adding the sodium borohydride into the solution, keeping stirring for 2 hours after dropwise adding, carrying out suction filtration on the solution, washing the solution with 1L of deionized water at 80 ℃, and placing the obtained filter cake for 12 hours at 80 ℃; taking out the solid powder, storing under the condition of keeping away from light and drying to obtain the tin-manganese powder with different proportionsComposite oxide supported platinum catalysts, i.e. Pt/Sn x Mn 1 O y A catalyst.
The performance test method of the tin-manganese composite oxide supported platinum catalyst with different proportions comprises the following steps:
step one, sequentially adding 50mg of Pt/Sn into a polytetrafluoroethylene lining of an intermittent high-pressure reaction kettle x Mn 1 O y Catalyst, magneton, then add 4.00mmol or 6.00mmol levulinic acid and 10ml dioxane;
step two, after the reaction kettle is installed, purging with argon for three times, extracting vacuum, connecting the reaction kettle with a hydrogen steel cylinder, introducing 0.5MPa hydrogen for purging for three times, and raising the pressure of the hydrogen to keep the pressure in the kettle at 2.0MPa;
step three, placing the reaction kettle into a preset oil bath kettle which is stable at 120 ℃, and simultaneously starting magnetic stirring at the rotating speed of 900rpm;
and step four, starting timing when the temperature in the kettle reaches 120 ℃, taking out the reaction kettle after the reaction lasts for 6 hours, cooling the reaction kettle for 10 minutes by using an ice water bath, releasing gas in the kettle, sucking reaction liquid in the kettle by using an injector, filtering the reaction liquid by using a 0.45-micrometer filter head, diluting the filtrate, and quantitatively analyzing the filtrate by using a Saimei Fei TRACE 1310 type gas chromatograph. Among them, the Sammerfue TRACE 1310 type gas chromatograph is equipped with a TR-5 capillary chromatographic column and an FID detector.
The results of the performance test of the tin-manganese composite oxide supported platinum catalyst with different proportions are shown in tables 1 and 2.
TABLE 1Pt/Sn x Mn 1 O y Catalyst performance test meter
TABLE 2Pt/Sn x Mn 1 O y Catalyst performance test meter
As can be seen from the performance test results of tables 1 and 2, pt/Sn prepared by the present invention x Mn 1 O y The catalyst, the introduction of tin in the composite oxide carrier greatly improves the conversion rate of levulinic acid, and the catalyst realizes the best catalytic effect when the molar ratio of tin to manganese is 0.8>99％；Pt/Sn 0.8 Mn 1 O y The catalyst has high catalytic activity under the reaction condition of levulinic acid with higher concentration (6 mmol), so that Pt/Sn is used 0.8 Mn 1 O y As the preferred optimum ratio catalyst.
Example 2: pt/Sn 0.8 Mn 1 O y The recycling experiment of the catalyst specifically comprises the following steps:
s1, adding Pt/Sn obtained in the fourth step of the example 1 0.8 Mn 1 O y Collecting reaction liquid after the catalyst participates in the performance test, performing suction filtration, alternately washing with deionized water and ethanol, and placing the obtained filter cake for 12 hours at 80 ℃; taking out the solid powder, and storing under the condition of keeping out of the sun and drying to obtain the Pt/Sn with the use frequency of 1 0.8 Mn 1 O y A catalyst.
Pt/Sn with number of times of use of 1 0.8 Mn 1 O y The performance test method of the catalyst comprises the following steps:
step one, sequentially adding 50mg of Pt/Sn into a polytetrafluoroethylene lining of an intermittent high-pressure reaction kettle 0.8 Mn 1 O y Catalyst, magneton, then add 4.00mmol levulinic acid and 10ml dioxane;
step two, after the reaction kettle is installed, purging with argon for three times, extracting vacuum, connecting the vacuum with a hydrogen steel cylinder, introducing 0.5MPa hydrogen for purging for three times, and increasing the pressure of the hydrogen to keep the pressure in the kettle at 2.0MPa;
step three, placing the reaction kettle into a preset oil bath kettle which is stable at 120 ℃, and simultaneously starting magnetic stirring at the rotating speed of 900rpm;
step four, starting to count when the temperature in the kettle reaches 120 DEG CAnd (3) taking out the reaction kettle after the reaction lasts for 6 hours, cooling the reaction kettle for 10min by using an ice water bath, releasing gas in the kettle, sucking reaction liquid in the kettle by using an injector, filtering the reaction liquid by using a 0.45-micron filter head, diluting the filtrate, and quantitatively analyzing the diluted filtrate by using a Sammer-FerTRACE 1310 type gas chromatograph. Among them, the SaimefeTRACE 1310 gas chromatograph is equipped with a TR-5 capillary column and an FID detector. Then repeating the above operations to obtain Pt/Sn with the use frequency of 2,3 0.8 Mn 1 O y The results of the catalyst performance test are shown in Table 3.
TABLE 3Pt/Sn 0.8 Mn 1 O y Experimental results of catalyst recycle
From the recycling results in Table 3, it can be seen that Pt/Sn 0.8 Mn 1 O y The catalyst has good cyclic availability and stability, and also has good catalytic performance and selectivity after being used for 3 times>99 percent. Therefore, pt/Sn 0.8 Mn 1 O y The catalyst has good recycling availability.
Example 3: sn (tin) 0.8 Mn 1 O y The preparation method of the noble metal catalyst with different carrier loads comprises the following steps:
s1, on a magnetic stirrer with the rotating speed of 550rpm, 1.81g of SnCl with the mass molar concentration of 4.42mmol/g 2 ·2H 2 O and 2.51g Mn (NO) with a molarity of 3.98mmol/g 3 ) 2 ·4H 2 Dissolving O in 100ml of methanol, and stirring to obtain a uniform solution;
s2, adding triethylamine into the uniform solution in the S1 dropwise, uniformly precipitating until the pH of the solution is =9, then adding 50ml of deionized water, controlling the temperature of the suspension at 65 ℃ and carrying out aging treatment for 18h;
s3, pouring the aged suspension into a sand core funnel, performing suction filtration, washing with deionized water until the pH of the filter cake is =7, and drying the obtained filter cake at 110 ℃ overnight;
s4, in S3Grinding the filter cake into powder, roasting for 4 hours at 400 ℃ in a muffle furnace at the heating rate of 2 ℃/min, taking out after cooling to room temperature to obtain Sn 0.8 Mn 1 O y A carrier;
s5, under the light-tight condition, under the magnetic stirring at the rotation speed of 550rpm, weighing 6mg of polyvinylpyrrolidone, dissolving in 0.6ml of water, adding into 150ml of water, and then respectively transferring 1.00ml of different noble metal precursor solutions (chloroauric acid solution, chloropalladic acid solution, hexachloroplatinic acid solution, ruthenium trichloride solution, iridium trichloride solution and silver nitrate solution) with the concentration of 4.76mg/ml for rapid addition; stirring for 15min;
s6, weighing Sn prepared in 238mg S4 0.8 Mn 1 O y Respectively adding the carrier into the mixed solution in the S5, then weighing 20mg of sodium borohydride, dissolving the sodium borohydride in 4.8ml of water, then respectively dropwise adding the sodium borohydride into the solution, keeping stirring for 2 hours after dropwise adding, carrying out suction filtration on the solution, washing the solution with 1L of deionized water at 80 ℃, and placing the obtained filter cake for 12 hours at 80 ℃; taking out the solid powder, and storing under the condition of keeping out of the sun and drying; sn is respectively prepared according to different noble metal solutions added in S5 0.8 Mn 1 O y Supported by different noble metal catalysts, i.e. Au/Sn 0.8 Mn 1 O y ，Pd/Sn 0.8 Mn 1 O y ，Pt/Sn 0.8 Mn 1 O y ，Ru/Sn 0.8 Mn 1 O y ，Ir/Sn 0.8 Mn 1 O y ，Ag/Sn 0.8 Mn 1 O y A catalyst.
Sn 0.8 Mn 1 O y The performance test method of the noble metal catalyst with different carrier loads comprises the following steps:
step one, using Pt/Sn 0.8 Mn 1 O y Catalyst for example, 50mg of Pt/Sn was added to the polytetrafluoroethylene lining of a batch autoclave reactor 0.8 Mn 1 O y Catalyst, magneton, then add 4.00mmol levulinic acid and 10ml dioxane;
step two, after the reaction kettle is installed, purging with argon for three times, extracting vacuum, connecting the vacuum with a hydrogen steel cylinder, introducing 0.5MPa hydrogen for purging for three times, and increasing the pressure of the hydrogen to keep the pressure in the kettle at 2.0MPa;
step three, placing the reaction kettle into a preset oil bath kettle which is stable at 120 ℃, and simultaneously starting magnetic stirring at the rotating speed of 900rpm;
and step four, starting timing when the temperature in the kettle reaches 120 ℃, taking out the reaction kettle after the reaction lasts for 6 hours, cooling the reaction kettle for 10 minutes by using an ice water bath, releasing gas in the kettle, sucking reaction liquid in the kettle by using an injector, filtering the reaction liquid by using a 0.45-micrometer filter head, diluting the filtrate, and quantitatively analyzing the filtrate by using a Saimei Fei TRACE 1310 type gas chromatograph. Among them, the SaimefeTRACE 1310 gas chromatograph is equipped with a TR-5 capillary column and an FID detector.
Sn 0.8 Mn 1 O y The results of the catalytic performance tests of the noble metal catalysts supported on the carrier are shown in table 4.
TABLE 4Sn 0.8 Mn 1 O y Catalytic performance test meter for noble metal catalysts with different carrier loads
As can be seen from the reaction results in Table 4, when Sn is present 0.8 Mn 1 O y When the carrier loads Au, ir and Ag, the catalyst does not work almost; selectivity of catalyst when Pd, ru are supported>99%, but the conversion is very low; the catalyst achieves the best catalytic effect only when Pt is loaded, completely converts 4mmol of levulinic acid under mild conditions and very low Pt loading, and has selectivity>99 percent. Therefore, pt/Sn is used 0.8 Mn 1 O y The catalyst is preferably the most preferable catalyst.
Example 4:
Pt/Sn 0.8 Mn 1 O y catalyst and process for preparing sameThe different reduction treatment methods of (1) specifically comprise the following steps:
s1, on a magnetic stirrer rotating at 550rpm, adding 1.81g of SnCl with the mass molar concentration of 4.42mmol/g 2 ·2H 2 O and 2.51g Mn (NO) with a molal mass concentration of 3.98mmol/g 3 ) 2 ·4H 2 Dissolving O in 100ml of methanol, and stirring to obtain a uniform solution;
s2, adding triethylamine into the uniform solution in the S1 dropwise, uniformly precipitating until the pH of the solution is =9, then adding 50ml of deionized water, controlling the temperature of the suspension at 65 ℃ and carrying out aging treatment for 18h;
s3, pouring the aged suspension into a sand core funnel, performing suction filtration, washing with deionized water until the pH of the filter cake is =7, and drying the obtained filter cake at 110 ℃ overnight;
s4, grinding the filter cake in the S3 into powder, roasting for 4 hours at 400 ℃ in a muffle furnace at the heating rate of 2 ℃/min, taking out after cooling to room temperature to prepare Sn 0.8 Mn 1 O y A carrier;
s5, under the condition of keeping out of the sun and under the magnetic stirring at the rotation speed of 550rpm, weighing 6mg of polyvinylpyrrolidone, dissolving in 0.6ml of water, adding into 150ml of water, and then transferring 1.00ml of hexachloroplatinic acid solution with the concentration of 4.76mg/ml for rapid addition; stirring for 15min;
s6, weighing Sn prepared in 238mg S4 0.8 Mn 1 O y Adding a carrier into the mixed solution in the S5, then weighing 20mg of sodium borohydride, dissolving the sodium borohydride in 4.8ml of water, dropwise adding the sodium borohydride into the solution, keeping stirring for 2 hours after dropwise adding, carrying out suction filtration on the solution, washing the solution with 1L of deionized water at 80 ℃, and placing the obtained filter cake for 12 hours at 80 ℃; taking out the solid powder, and storing the solid powder under the dark drying condition to obtain the Pt/Sn subjected to sodium borohydride reduction treatment 0.8 Mn 1 O y A catalyst.
S7, weighing Sn prepared in 238mg S4 0.8 Mn 1 O y Adding the carrier into the mixed solution in the S5, stirring for 2h, performing suction filtration, washing with 1L of deionized water at 80 ℃, and placing the obtained filter cake at 80 ℃ for 12h; taking out the solid powder for later use;
s8, mixing the solid powder in the S7Adding into a 250ml three-neck bottle, adding magneton and 25ml ethylene glycol, refluxing in an oil bath kettle at 140 ℃, starting magnetic stirring at the rotation speed of 600rpm, and introducing argon for protection; reducing for 4h, cooling to room temperature, filtering the solution, washing with 0.5L deionized water, and standing the obtained filter cake at 80 deg.C for 12h; taking out the solid powder, storing under the condition of keeping away from light and drying to obtain the Pt/Sn after the reduction treatment of the ethylene glycol 0.8 Mn 1 O y A catalyst;
s9, placing the powder obtained in the step S7 in a tubular furnace, introducing hydrogen, carrying out reduction treatment for 0.5h at 350 ℃, wherein the hydrogen flow rate is 20ml/min, the temperature rise rate of the tubular furnace is 5 ℃/min, taking out solid powder after the tubular furnace is cooled to room temperature, and storing the solid powder under the condition of drying in the dark to obtain the Pt/Sn subjected to hydrogen reduction treatment 0.8 Mn 1 O y A catalyst.
Pt/Sn of different reduction treatment methods 0.8 Mn 1 O y The performance test method of the catalyst comprises the following steps:
step one, using Pt/Sn 0.8 Mn 1 O y Taking the catalyst as an example, 50mg of the catalyst and magnetons are added in sequence into a polytetrafluoroethylene lining of a batch type high-pressure reaction kettle, and then 4.00mmol of levulinic acid and 10ml of dioxane are added;
step two, after the reaction kettle is installed, purging with argon for three times, extracting vacuum, connecting the reaction kettle with a hydrogen steel cylinder, introducing 0.5MPa hydrogen for purging for three times, and raising the pressure of the hydrogen to keep the pressure in the kettle at 2.0MPa;
step three, placing the reaction kettle into a preset oil bath kettle which is stable at 120 ℃, and simultaneously starting magnetic stirring at the rotating speed of 900rpm;
and step four, starting timing when the temperature in the kettle reaches 120 ℃, taking out the reaction kettle after the reaction lasts for 6 hours, cooling the reaction kettle for 10 minutes by using an ice water bath, releasing gas in the kettle, sucking reaction liquid in the kettle by using an injector, filtering the reaction liquid by using a 0.45-micrometer filter head, diluting the filtrate, and quantitatively analyzing the filtrate by using a Saimei Fei TRACE 1310 type gas chromatograph. Among them, the SaimefeTRACE 1310 gas chromatograph is equipped with a TR-5 capillary column and an FID detector.
Pt/Sn of different reduction treatment methods 0.8 Mn 1 O y The results of the catalyst performance tests, as shown in table 5,
TABLE 5 Pt/Sn for different reduction treatment methods 08 Mn 1 O y Catalytic performance test meter for catalyst
As can be seen from the reaction results in Table 5, when Pt/Sn was subjected to reduction treatment using hydrogen gas 0.8 Mn 1 O y In the process, the catalyst does not work almost, and the valence state of tin is possibly influenced by violent reduction conditions, so that the strong interaction between the noble metal platinum and the metal carrier tin element is influenced; when Pt/Sn is subjected to reduction treatment by using ethylene glycol 0.8 Mn 1 O y Selectivity of the catalyst>99%, but the conversion was very low; when reduction treatment of Pt/Sn by sodium borohydride is used 0.8 Mn 1 O y The catalyst realizes the best catalytic effect, completely converts 4mmol of levulinic acid under mild conditions and has selectivity>99 percent. So that the Pt/Sn after reduction treatment by sodium borohydride 0.8 Mn 1 O y Catalysts are preferred as the best catalysts.
The terms of the invention are explained:
(1) Levulinic acid: also called levo-sugar acid, is a polyfunctional compound simultaneously containing carbonyl, alpha-hydrogen and carboxyl, and is easily soluble in water and partial organic solvents. The distillation under normal pressure hardly decomposes, and the unsaturated gamma-lactone is formed by dehydration after long-term heating. Is a basic raw material for synthesizing various light chemical products, and has wide use value in organic synthesis, industry, agriculture and medicine industries.
(2) Gamma-valerolactone: also known as 4-methylbutyrolactone, is one of the most promising platform molecules for the sustainable production of fuels and value-added chemicals, and can be used as a precursor for gasoline and diesel fuels, as a green solvent in fine chemical synthesis and food additives, and as an intermediate for the synthesis of some value-added chemicals, such as 1, 4-pentanediol and methyl pentenoate. Has vanillin and coconut fragrance, and is edible spice which is allowed to be used in China GB 2760-86.
(3) Catalytic hydrogenation: in the presence of a catalyst, unsaturated organic compounds such as alkene and alkyne and hydrogen molecules are subjected to addition reaction to generate corresponding saturated organic compounds. The mechanism of catalytic hydrogenation is to reduce the activation energy of the reaction, change the reaction rate, and add the active hydrogen atoms generated by the hydrogen molecules adsorbed on the catalyst to unsaturated organic compounds such as alkene or alkyne.
(4) And (3) hydrogenolysis: while hydrogen reacts with organic compounds, the chemical bonds are broken, and the hydrogenation reaction is also called hydrogenolysis reaction and comprises hydrodealkylation, hydrocracking, hydrodesulfurization and the like. Hydrogenolysis generally refers to the reaction of a carbon-heteroatom (or carbon-carbon bond) bond in a reduction reaction to break, and the hydrogen replaces the leaving heteroatom (carbon atom) or group to form the corresponding hydrocarbon. The hydrogenolysis reaction mainly uses a catalytic hydrogen method.
(5) The supported catalyst: is a catalyst with uniformly dispersed active components and loaded on a specially selected carrier. Because the carrier can provide an effective surface and a proper pore structure, the sintering and aggregation of the active components can be greatly reduced, and the mechanical strength of the catalyst is enhanced; there is also a strong interaction between the active component and the support, so supported catalysts generally exhibit excellent performance.
The above description is only a part of specific embodiments of the present invention (since the formula of the present invention belongs to the numerical range, the embodiments are not exhaustive, and the protection scope of the present invention is subject to the numerical range and other technical point ranges), and the detailed contents or common knowledge known in the schemes are not described too much. It should be noted that the above-mentioned embodiments do not limit the present invention in any way, and it is obvious for those skilled in the art that all the technical solutions obtained by using the equivalent substitution or the equivalent change fall within the protection scope of the present invention. The scope of the claims of the present application shall be defined by the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (6)
1. The application of levulinic acid in preparing gamma-valerolactone by catalytic hydrogenation is characterized in that the adopted catalyst is a tin-manganese composite oxide loaded nano platinum catalyst, in particular Pt/Sn x Mn 1 O y A catalyst; the Pt/Sn x Mn 1 O y The catalyst is Pt/Sn 0.8 Mn 1 O y A catalyst; the Pt/Sn 0.8 Mn 1 O y The catalyst is reduced by sodium borohydride;
the preparation method of the catalyst comprises the following steps:
s1, snCl 2 ·2H 2 O and Mn (NO) 3 ) 2 ·4H 2 Dissolving O in methanol, and stirring to obtain a uniform solution;
s2, adding triethylamine into the uniform solution in the S1, uniformly precipitating, adding deionized water, and then controlling the temperature of the suspension and carrying out aging treatment;
s3, carrying out suction filtration on the aged suspension, washing to obtain a neutral filter cake, and then drying;
s4, grinding the filter cake in the S3, roasting, and cooling to room temperature to obtain Sn x Mn 1 O y A carrier;
s5, under the light-tight condition, dropwise adding hexachloroplatinic acid solution into the polyvinylpyrrolidone aqueous solution, and violently stirring;
s6, sn prepared in S4 x Mn 1 O y Adding a carrier into the mixed solution in the S5, immediately dropwise adding a sodium borohydride solution, stirring after dropwise adding, carrying out suction filtration and washing on the solution, and placing a filter cake at a high temperature; taking out the solid powder, and then taking out the solid powder, storing under the condition of keeping out of the sun and drying to prepare Pt/Sn x Mn 1 O y A catalyst.
2. The use of claim 1, wherein in step S2, triethylamine is added dropwise to the homogeneous solution in S1 to a solution pH =9, and deionized water is added, and the suspension is kept at a temperature of 55-75 ℃ and aged for at least 12h.
3. The use according to claim 1, wherein in S3, the aged suspension is poured into a sand core funnel, filtered, washed with deionized water to a solution pH =7, and after washing, the filter cake is dried at 100-120 ℃ for 8-14h; in S6, washing a filter cake by using deionized water at 70-90 ℃ during suction filtration, and standing the obtained filter cake at 70-90 ℃ for 10-14h after washing.
4. The use according to claim 1, wherein in S4, the filter cake in S4 is ground into powder and then calcined in a muffle furnace at 400 ℃ for 4h, wherein the temperature rise rate is 2 ℃/min.
5. The method for testing the performance of a catalyst in an application according to claim 1, wherein the method comprises the steps of:
step one, sequentially adding the tin-manganese composite oxide load nano platinum catalyst prepared in the step 6, magnetons, levulinic acid and dioxane into a polytetrafluoroethylene lining of an intermittent high-pressure reaction kettle;
step two, after the reaction kettle is installed, purging with argon for three times, extracting vacuum, connecting the vacuum with a hydrogen steel cylinder, introducing hydrogen for purging for three times, and raising the pressure of the hydrogen to keep the pressure in the kettle at 1.6-2.4MPa;
step three, putting the reaction kettle into an oil bath kettle with preset stable temperature, and simultaneously starting magnetic stirring;
and step four, starting timing when the temperature in the kettle reaches 120 ℃, taking out the reaction kettle after the reaction lasts for 4-8 hours, releasing gas in the kettle after cooling by using an ice water bath, sucking reaction liquid in the kettle by using an injector, filtering by using a micron filter head, diluting the filtrate, and then carrying out quantitative analysis by using a gas chromatograph.
6. The performance testing method of claim 5, wherein the performance testing method comprises the following parameters: hydrogen pressure: 2MPa; reaction temperature: 120 ℃; reaction time: 6h; solvent: 10mL dioxane.
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