CN111253347B - Method for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid - Google Patents
Method for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid Download PDFInfo
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Abstract
The invention relates to a method for preparing gamma-valerolactone by catalytically hydrogenating levulinic acid, namely levulinic acid in AgZrO 2 In aqueous phase under the action of GO catalystAnd carrying out selective hydrogenation reaction to generate gamma-valerolactone. By using AgZrO 2 The GO catalyst reacts in a water phase for 4 hours at 200 ℃ and 3MPa hydrogen pressure, the conversion rate of the levulinic acid can reach 100 percent, and the yield of the gamma-valerolactone>99 percent, and neither Ag nor Zr is precipitated. AgZrO 2 Ag in the GO catalyst is cheaper than noble metals such as Pt, Pd and the like, and is not separated out in the reaction process; ZrO (ZrO) 2 Is also stable in the aqueous solution of levulinic acid; after the graphene oxide is introduced into the catalyst, the catalyst obtains larger specific surface area and pore volume, and the metal Ag particles are not easy to fall off from the surface of the catalyst. And AgZrO without added graphene oxide 2 Catalyst phase AgZrO 2 Large specific surface area of GO catalyst, Ag and ZrO 2 Small crystal grains, firmer combination, higher catalytic activity and selectivity to the reaction and industrial application value.
Description
Technical Field
The invention relates to a method for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid, in particular to AgZrO 2 GO catalyst, a preparation method of the catalyst and application of the catalyst in preparation of gamma-valerolactone.
Background
At present, the large-scale use of fossil resources causes global warming, air pollution, energy shortage and other problems, and therefore, the development of green renewable energy has become a hot spot of future research. Biomass is the only renewable organic carbon resource with wide sources in nature, and can replace fossil resources to be converted into fuels and chemicals. The conversion of biomass into biomass-based platform compounds and further, the production of high value-added chemicals is an important strategy for biomass conversion. Levulinic acid is one of the 12 most important platform compounds screened by the U.S. department of energy. Levulinic acid can be obtained by hydrolyzing waste lignocellulose by using acid as a catalyst, and the method is industrially produced at present. Levulinic acid can be converted into various high value-added derivatives such as gamma-valerolactone, 2-methyl-tetrahydrofuran, 1, 4-pentanediol, angelica lactone and the like, wherein the gamma-valerolactone is rapidly concerned by researchers due to excellent physicochemical properties, low toxicity and safe storage performance. Gamma valerolactone has a wide range of uses in a variety of fields, and can be used as a fuel additive, a food ingredient, a medical intermediate, a higher olefin fuel, a green renewable solvent, a nylon intermediate and other commercial uses (e.g., lubricating oil and brake fluid). The key point of using levulinic acid to synthesize gamma-valerolactone is to develop a high-efficiency catalyst and reaction process conditions.
The catalysts for this reaction are currently classified into liquid catalysts and solid catalysts. The liquid catalyst has the defects that the catalyst is difficult to recycle and the like. Currently, the solid catalysts used in this field mainly include noble metal catalysts and non-noble metal catalysts. Some noble metal catalysts with Ru, Pd and Pt as active components and non-noble metal catalysts with Cu and Ni as active components can achieve better catalytic activity and product selectivity, but as levulinic acid is an organic acid, the levulinic acid can interact with metal cations in the catalysts to cause metal precipitation, and the precipitation is more serious when water is used as a solvent. Gundekari, s.; srinivasan, K.in situ generated Ni (0) @ boehmit from NiAl-LDH: An effective catalyst for selective hydrogenation of biological less organic acid to gamma-equivalent catalysts 2017,102,40-43 Ni/boehmit as a catalyst In water as a solvent at 200 ℃ at 4MPaH 2 Reacting for 6 hours under pressure, wherein the precipitation amount of Ni reaches 0.1-0.4% in each cycle reaction. Zhang, l.; mao, j.; li, S.; yin, j.; sun, x.; guo, x.; song, c.; zhou, J., Hydrogenation of legacy acid in gamma-valve of in situ reduced Cu biological catalyst, Strategy and mechanism of modifying Cu leaching applied catalysts B, Environmental 2018,232,1-10 reduction of pretreated Cu in hydrogen 0.8 /Al 2 O 3 -H 2 Catalyst, water as solvent, at 180 ℃ in 4MPaH 2 The reaction was carried out under pressure for 1 hour, and the amount of Cu deposited reached 114.1 ppm. Hengne A M, Rode C V, Cu-ZrO 2 nanocomposition catalyst for selective hydrogenation of leutinic acid and its ester to gamma-valerolactone, Green Chemistry,2012,14(4):1064-1072 employs Cu/Al reduced in a hydrogen atmosphere at 350 ℃ 2 O 3 And Cu/ZrO 2 Catalyst in water as solvent at 3.45MPaH 2 The reaction was carried out under pressure for 5 hours, and the amounts of Cu deposited were 174ppm and 34ppm, respectively. Although the prior conversion of levulinic acid into an ester or the reaction in an organic solvent such as alcohol or tetrahydrofuran can suppress the precipitation of metal to some extent, water is inevitable as a by-product of the production of γ -valerolactone from LA. Therefore, a catalyst resistant to metal precipitation should be constructed based on an aqueous solvent system.
The structure of the catalyst has a significant impact on the catalyst performance. For example, a catalyst with a large specific surface area can provide more catalytically active sites for the reaction, thereby reducing the amount of catalyst used or increasing the conversion rate. In addition, the stability of the active components of the catalyst is also related to the structure. Through the 'bonding' effect of the structural auxiliary agent, the active component is not easy to fall off, thereby improving the stability of the catalyst.
In order to overcome the defects and shortcomings of the prior art, the invention provides a novel catalyst for preparing gamma-valerolactone by selective hydrogenation of LA. The catalyst takes cheap noble metal Ag as a hydrogenation active component and takes ZrO 2 Is an acid catalytic component, takes Graphene Oxide (GO) as an auxiliary agent, and is compounded into AgZrO by adopting a coprecipitation method 2 a/GO catalyst. AgZrO 2 the/GO catalyst can be used for aqueous phase reaction without high-temperature pre-reduction treatment, and Ag and Zr components are not separated out in the reaction process. Under the modulation of GO, AgZrO 2 Specific surface area of/GO catalyst (221 m) 2 /g) AgZrO without added GO 2 Catalyst (43 m) 2 5 times of the amount of the compound,/g). Reacting in water solvent under the conditions of 3MPa hydrogen pressure and 200 ℃ for 4h, wherein AgZrO 2 The GO catalyst can completely convert LA, the yield of gamma-valerolactone is close to 100 percent, and AgZrO 2 The catalyst can only convert 33% of the LA.
Disclosure of Invention
The invention provides AgZrO for overcoming the defects of the prior art 2 Catalyst for the catalytic addition of/GO and catalytic addition thereofA method for preparing gamma-valerolactone from hydrogen levulinic acid.
The purpose of the invention is realized by the following technical scheme:
a process for preparing gamma-valerolactone by catalytic hydrogenation of acetylpropionic acid features use of AgZrO 2 A GO catalyst having the following composition and preparation:
the catalyst comprises silver (Ag) and zirconium dioxide (ZrO) 2 ) A nanomaterial compounded with Graphene Oxide (GO),
the metal Ag provides a hydrogenation catalysis function for the catalyst,
ZrO 2 provides the acid catalysis function for the catalyst,
GO provides the function of a structural promoter for the catalyst.
The catalyst is prepared by adopting a coprecipitation method, and comprises the following specific steps:
preparation of salt solution: dispersing a certain amount of paste graphene oxide in deionized water, performing ultrasonic treatment for 30min, and respectively taking a certain amount of AgNO 3 And Zr (NO) 3 ) 4 ·5H 2 O, adding the solution into the liquid in which the graphene oxide is dispersed, and stirring to dissolve the salt to prepare a salt solution;
preparing a precipitator: dissolving NaOH in deionized water to prepare 0.2M NaOH solution;
③ coprecipitation: placing a salt solution containing graphene oxide on a magnetic stirrer, stirring at 1000rpm, dropwise adding an alkali solution into the salt solution, measuring the pH value of the solution by using a pH meter, stopping dropwise adding the alkali solution until the pH value is about 12, continuing stirring for 4h, turning off the stirring, and aging for 12 h;
fourthly, suction filtration: filtering the solution by using a Buchner funnel, and washing a filter cake by using ethanol until the filter cake is neutral;
drying: putting the filter cake in a vacuum drying oven for drying for 12h at the temperature of 80 ℃, and grinding the filter cake into powder by using an agate mortar;
sixthly, roasting: placing the prepared powdery sample in a tubular heating furnace, raising the temperature from room temperature to 500 ℃ by a program of 10 ℃/min under the protection of nitrogen, roasting for 2 hours at the constant temperature of 500 ℃, stopping introducing nitrogen when the temperature is reduced to the room temperature, taking out the sample, and sealing and storing.
Configuration of AgNO 3 And Zr (NO) 3 ) 4 ·5H 2 When in O salt solution, the molar ratio of Ag to Zr is 1: 9-4: 6, preferably 2: 8; the amount of the added graphene oxide accounts for (Ag + ZrO) 2 ) 5-30% of the total mass, preferably 10%.
After 10% of GO is introduced into the catalyst, the specific surface area of the catalyst is 5 times that of the catalyst without GO, the reaction activity is improved by 3 times, and the Ag component and ZrO in the catalyst are made by GO 2 The bond is tighter.
Prepared AgZrO 2 The GO catalyst can generate catalytic activity in a water solvent without hydrogen reduction pretreatment, and the selectivity of gamma-valerolactone is close to 100%.
Active components Ag and Zr can not be separated out in the water phase reaction.
The method takes water as a solvent, the temperature of the levulinic acid hydrogenation reaction is 180-220 ℃, and the hydrogen pressure is 3-5 MPa. More preferably, the yield of the gamma-valerolactone can reach 99.3 percent under the conditions that the reaction temperature is 220 ℃, the hydrogen pressure is 4MPa and the reaction time is 6 hours.
Compared with the prior art, the invention has the following advantages and effects: the catalyst has the advantages that the catalytic effect of the catalyst can be obviously improved by adding a small amount of graphene oxide, active components can be well dispersed, the specific surface area is improved, the precipitation of metal Ag can be inhibited, and the stability of the carrier is maintained. AgZrO 2 The active metal component Ag of the/GO catalyst is not separated out in the reaction. ZrO (ZrO) 2 Do not react with LA. For with Al 2 O 3 Supported catalysts, since LA can react with Al 2 O 3 The catalyst structure is destroyed due to the reaction, and the catalyst is swelled after the reaction. And ZrO 2 It is stable in aqueous LA solution and the catalyst is not swollen after the reaction. So AgZrO 2 the/GO catalyst can adapt to a water solvent reaction system. Although Ag is a noble metal, it is a cheap noble metal compared with Au, Pt, Pd, Ru, etc., and AgZrO 2 the/GO catalyst does not need to be subjected to high-temperature pre-reduction treatment and can not be inactivated due to oxidation. AgZrO 2 the/GO catalyst is prepared by adopting a coprecipitation method, and the preparation method is simple and suitable for large-scale industrial preparation. AgZrO at reaction temperature below 220 deg.C 2 the/GO catalyst can not dissociate C-C bonds, so that the decomposition of gamma-valerolactone can not be caused, and the catalyst can be used for preparing the catalyst at the temperature of 220 ℃ and the H pressure of 4MPa 2 And under the condition of 6 hours, the yield of the gamma-valerolactone can reach 99.3 percent, and the gamma-valerolactone has high selectivity.
Drawings
FIG. 1 projection Electron microscope (TEM) and high resolution projection Electron microscope (HRTEM) in which (a) AgZrO 2 (2:8) GO 10% TEM; (b) AgZrO 2 TEM of (2: 8); (c) AgZrO 2 (2:8) HRTEM of GO 10% and (d) AgZrO 2 HRTEM of (2:8)
FIG. 2AgZrO 2 (2:8) GO 10% and AgZrO 2 (2:8) nitrogen physisorption-desorption isotherm curve.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1 AgZrO 2 (2:8) batch reaction in aqueous GO 10% catalyst phase
1. The catalyst is prepared by adopting a coprecipitation method, and comprises the following specific steps:
(1) preparation of salt solution: taking paste graphene oxide containing 86.6mg of dry basis weight, dispersing in 144ml deionized water, performing ultrasonic treatment for 30min, and respectively taking 1.44mmol AgNO 3 And 5.76mmol of Zr (NO) 3 ) 4 ·5H 2 Dissolving graphene oxide dispersion liquid into salt solution;
(2) preparation of a precipitating agent: dissolving NaOH in deionized water to prepare 0.2M NaOH solution;
(3) coprecipitation: placing a salt solution containing graphene oxide on a magnetic stirrer, stirring at 1000rpm, dropwise adding an alkali solution into the salt solution, measuring the pH value of the solution by using a pH meter, stopping dropwise adding the alkali solution until the pH value is about 12, continuing stirring for 4h, turning off the stirring, and aging for 12 h;
(4) and (3) suction filtration: filtering the solution by using a Buchner funnel, and washing a filter cake by using ethanol until the filter cake is neutral;
(5) and (3) drying: drying the filter cake obtained in the step (4) in a vacuum drying oven at 80 ℃ for 12 hours, and grinding the filter cake in an agate mortar to obtain powder;
(6) roasting: and (3) putting the powdery sample prepared in the step (5) into a U-shaped tube, putting the U-shaped tube into a tube furnace, raising the temperature by a program of 10 ℃/min from room temperature to 500 ℃, roasting the powder at the constant temperature of 500 ℃ for 2 hours, taking out the sample when the temperature is reduced to the room temperature, and sealing and storing the sample.
The catalyst is marked as AgZrO 2 (2:8) GO 10%, wherein the ratio of Ag to Zr is 2:8, and the mass of GO accounts for Ag and ZrO 2 10% of the sum of the masses.
2. Reaction test: AgZrO testing by intermittent reaction 2 (2:8) the performance of catalyzing the hydrogenation reaction of levulinic acid by using GO 10% catalyst comprises the following specific steps:
(1) adding 200.0mg levulinic acid, 8ml water and 100mg AgZrO into a special magnetic stirring high-pressure reaction kettle 2 (2:8) GO 10% catalyst, screwing down the reaction kettle and checking the airtightness of the device, and introducing 3MPaH after ensuring the airtightness of the device 2 The reaction vessel was heated to raise the temperature to 200 ℃ at a stirring rate of 400rpm, and reacted at this temperature for 4 hours.
(2) After the reaction is finished, adding an internal standard substance into the reaction kettle, collecting a liquid-phase product, and recovering the catalyst through centrifugation. The reaction solution was detected by inductively coupled plasma emission spectrometry (ICP-OES, Optima7000DV, Perkin Elmer Ltd.). The liquid phase product was analyzed by gas chromatography.
Comparative example 1 AgZrO 2 (2:8) batch reaction in the aqueous phase of the catalyst
1. Preparing a catalyst: the same procedure as in example 1 was repeated except that GO was not added.
The catalyst is marked as AgZrO 2 (2:8), wherein the ratio of Ag to Zr is 2: 8.
2. Reaction test: except that the catalyst adopts AgZrO 2 (2:8), the other steps are the same as in example 1.
Table 1 reaction results of example 1 and comparative example 1.
The reaction conditions are as follows: 200 ℃ H 2 The pressure is 3MPa, the reaction time is 4h, and the solvent is water.
As can be seen from the results in Table 1, AgZrO after GO addition 2 (2:8) GO 10% enables complete conversion of levulinic acid, whereas AgZrO 2 (2:8) the conversion was only 33%. Indicating that the former has high catalytic activity. FIG. 1 shows AgZrO 2 (2:8) Ag and ZrO in GO 10% catalyst 2 Has a low degree of crystallinity and a small particle diameter, and is AgZrO 2 (2:8) larger Ag and ZrO in the catalyst 2 The particles of (1). The result of the nitrogen physical adsorption (figure 2) test shows that AgZrO 2 (2:8) the specific surface area and pore volume of GO 10% catalyst were 221m respectively 2 G and 0.31cm 3 G, and AgZrO 2 (2:8) the specific surface area and pore volume of the catalyst are only 43m 2 G and 0.17cm 3 (ii) in terms of/g. It can be seen that the catalyst component dispersion is improved after the GO is introduced.
TABLE 2 molar ratio of Ag to Zr on the surface of the catalyst obtained by X-ray photoelectron spectroscopy (XPS) analysis
Table 2 gives the XPS analyzed elemental composition of the catalyst surface. Fresh AgZrO 2 (2:8) the molar ratio of Ag to Zr on the surface of the catalyst is 14:100, the molar ratio of Ag to Zr is reduced to 2:100 after the reaction, the Ag content is about 15 percent of that of a fresh catalyst, and the AgZrO is shown 2 (2:8) the metallic Ag particles on the catalyst are unstable and can be peeled off from the surface of the catalyst. Fresh AgZrO 2 (2:8) the molar ratio of Ag to Zr on the surface of the GO catalyst is 14:100, the molar ratio of Ag to Zr after reaction is 13:100, and the content of Ag after reaction is similar to that of a fresh catalyst, which indicates that Ag is relatively stable. Therefore, after the graphene oxide is added, the Ag component in the catalyst is relatively stable and is not easy to sinter and fall off
Comparative example 2 AgAl 2 O 3 (2:8) batch reaction in aqueous GO 10% catalyst phase
1. Preparing a catalyst: except that Zr (NO) 3 ) 4 ·5H 2 Al (NO) for O 3 ) 3 ·9H 2 O, the same as example 1.
The catalyst is marked as AgAl 2 O 3 (2:8)GO10％。
2. And (3) reaction testing: except that the catalyst adopts AgAl 2 O 3 (2:8) GO 10%, the rest being the same as in example 1.
Comparative example 3 AgCo 2 O 3 (2:8) batch reaction in aqueous GO 10% catalyst phase
1. Preparing a catalyst: except that Zr (NO) 3 ) 4 ·5H 2 Co (NO) for O 3 ) 2 ·6H 2 O, the same as example 1.
The catalyst is marked AgCo 2 O 3 (2:8)GO10％。
2. Reaction test: except that the catalyst adopts AgCo 2 O 3 (2:8) GO 10%, the rest being the same as in example 1.
Table 3 reaction results of example 1 and comparative examples 2 and 3.
Reaction conditions are as follows: 200 ℃ H 2 The pressure is 3MPa, the reaction time is 4h, and the solvent is water.
As can be seen from the data in Table 3, AgAl 2 O 3 (2:8) GO 10% has Al precipitation and reaction activity inferior to AgZrO 2 (2:8)GO10％；AgCo 2 O 3 (2:8) GO 10% although 100% levulinic acid conversion was achieved, Co was heavily precipitated and gamma valerolactone selectivity was less than 99%. Comprehensive evaluation, AgZrO 2 (2:8) GO 10% has high catalytic activity, does not precipitate metal ions and shows excellent catalytic performance.
Example 2-10 AgZrO under different reaction conditions 2 (2:8) catalytic effect of GO 10%.
1. Preparing a catalyst: the same as in example 1.
2. Reaction test: the reaction solvent, reaction temperature, hydrogen pressure and reaction time of each example were set as listed in Table 4, and the others were the same as in example 1.
Table 4 reaction results of examples 1 to 10.
As shown in table 4, extending the reaction time, increasing the reaction temperature and hydrogen pressure all contribute to obtaining high conversion; even if the reaction is carried out for 6 hours, or at 220 ℃, or under 4MPa of hydrogen, the generated gamma-valerolactone product is still close to 100 percent, which indicates that the gamma-valerolactone is still at AgZrO 2 (2:8) GO 10% is very stable in the catalytic system. Except tetrahydrofuran, the reaction activity and/or the product yield in other solvents are not as good as those in water solvent. Tetrahydrofuran is an organic solvent, which is advantageous from a non-toxic economic standpoint, even if the same conversion and yield as water solvents are obtained. Water easily causes metal precipitation, but AgZrO 2 (2:8) metal ions are not separated out from GO 10% in a water solvent system, high activity and high yield can be obtained, and the catalyst is an ideal catalyst for catalyzing levulinic acid to prepare gamma-valerolactone in a water phase.
Claims (4)
1. The method for preparing gamma-valerolactone by catalytically hydrogenating levulinic acid is characterized in that AgZrO is adopted for catalytic hydrogenation reaction 2 The GO catalyst takes water or tetrahydrofuran as a solvent, the levulinic acid hydrogenation reaction temperature is 180-220 ℃, and the hydrogen pressure is 3-5 MPa; preparation of the AgZrO 2 The GO catalyst comprises the following specific steps:
preparation of salt solution: dispersing a certain amount of paste graphene oxide in deionized water, performing ultrasonic treatment for 30min, and respectively taking a certain amount of AgNO 3 And Zr (NO) 3 ) 4 ·5H 2 O, adding the solution into the liquid in which the graphene oxide is dispersed, and stirring to dissolve the salt to prepare a salt solution; wherein, AgNO is prepared 3 And Zr (NO) 3 ) 4 ·5H 2 When the salt solution is O, the molar ratio of Ag to Zr is 1: 9-4: 6; the amount of the added graphene oxide accounts for Ag and ZrO 2 5% -30% of the total mass;
preparing a precipitator: dissolving NaOH in deionized water to prepare 0.2M NaOH solution;
③ coprecipitation: placing a salt solution containing graphene oxide on a magnetic stirrer, stirring at 1000rpm, dropwise adding an alkali solution into the salt solution, measuring the pH value of the solution by using a pH meter, stopping dropwise adding the alkali solution until the pH =12, continuing stirring for 4h, turning off the stirring, and aging for 12 h;
fourthly, suction filtration: filtering the solution by using a Buchner funnel, and washing a filter cake by using ethanol until the filter cake is neutral;
drying: putting the filter cake in a vacuum drying oven for drying for 12h at the temperature of 80 ℃, and grinding the filter cake into powder by using an agate mortar;
sixthly, roasting: placing the prepared powdery sample in a tubular heating furnace, raising the temperature from room temperature to 500 ℃ by a program of 10 ℃/min under the protection of nitrogen, roasting for 2 hours at the constant temperature of 500 ℃, stopping introducing nitrogen when the temperature is reduced to the room temperature, taking out the sample, and sealing and storing.
2. The method for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid according to claim 1, wherein AgNO is prepared 3 And Zr (NO) 3 ) 4 ·5H 2 When the salt solution is O, the molar ratio of Ag to Zr is 2: 8; the amount of the added graphene oxide accounts for Ag and ZrO 2 10% of the total mass.
3. The method for preparing gamma-valerolactone by catalytically hydrogenating levulinic acid according to claim 1, wherein the catalytic hydrogenation reaction takes water as a solvent.
4. The method for preparing gamma-valerolactone by catalytically hydrogenating levulinic acid according to claim 1, wherein the levulinic acid hydrogenation reaction temperature is 220 ℃, the hydrogen pressure is 4MPa, and the reaction is carried out for 6 hours.
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