CN115974820B - Method for preparing furfuryl alcohol by hydrogenating furfural - Google Patents
Method for preparing furfuryl alcohol by hydrogenating furfural Download PDFInfo
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 49
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000002086 nanomaterial Substances 0.000 claims abstract description 17
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- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000004873 anchoring Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000012528 membrane Substances 0.000 claims abstract 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000011068 loading method Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
A method for preparing furfuryl alcohol by hydrogenation of furfural comprises the steps of using a platinum-containing hybrid nano-structure catalyst, and catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol under the conditions of a reaction solvent, a certain hydrogen pressure and a certain reaction temperature; the platinum-containing hybrid nano-structure catalyst is Pt/@ -FeO x SBA-15 catalyst; the preparation method of the platinum-containing hybrid nano-structure catalyst comprises the following steps: first, feO is precipitated x Coating a membrane layer on the SBA-15 molecular sieve, washing, filtering, drying and calcining to obtain the composite carrier FeO x SBA-15, and anchoring Pt nano particles on composite carrier FeO by photochemical reduction method x and/SBA-15 to obtain the platinum-containing hybrid nano-structure catalyst. The catalyst provided by the invention has excellent catalytic activity when being used for catalyzing furfuralcohol prepared by selective hydrogenation of furfural, and under mild reaction conditions, the conversion rate and selectivity of furfural can reach 100%.
Description
Technical Field
The invention belongs to the technical field of catalytic hydrogenation, and particularly relates to a method for preparing furfuryl alcohol by hydrogenating furfural.
Background
Furfuryl alcohol is an important organic chemical raw material and a fine chemical raw material, and is usually prepared by deep processing of furfural. Because of its excellent chemical properties, mechanical resistance and thermal stability, it is widely used in the production of furan resins (such as furan phenolic resins) and plasticizers, and plasticizers synthesized from furfuryl alcohol as a raw material exhibit extremely excellent cold resistance, and at the same time, furfuryl alcohol is also widely used in various fields such as synthetic fibers, rubber, pesticides, etc. Along with the continuous development of manufacturing industry, the market demand of furfuryl alcohol is further expanded, china is the largest furfural production and export country in the world, and renewable resources are fully utilized, so that not only can economic benefit be improved, but also the problem of energy crisis can be relieved. There is therefore an urgent need to develop efficient and environmentally friendly catalysts for catalyzing the selective hydrogenation of furfural to furfuryl alcohol.
In the method for preparing furfuryl alcohol by using furfural, the main byproducts of the Connizzaro method account for half of the total amount of the main byproducts, the solvent is more consumed, and the separation is troublesome, so that the normal pressure method and the high pressure method are mainly used in industry, and the two methods can react only at a higher temperature or pressure, so that an efficient and environment-friendly catalyst needs to be developed to promote the production of furfuryl alcohol.
There is a patent that discloses a Cu-Cr catalyst containing a noble metal Pt, which has a high catalytic activity but requires severe reaction conditions and pollutes the environment.
Therefore, the catalyst which has mild catalytic reaction conditions, is efficient and environment-friendly and has important significance for catalyzing the hydrogenation of the furfural.
Disclosure of Invention
The invention aims to provide a method for preparing furfuryl alcohol by hydrogenating furfural, which aims to solve the problem that the furfuryl alcohol prepared by the prior furfural in the background art can be reacted only at a higher temperature or pressure.
In order to achieve the above purpose, the invention provides a method for preparing furfuryl alcohol by hydrogenating furfural, which comprises the steps of using a platinum-containing hybrid nano-structure catalyst, and catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol under the conditions of a reaction solvent, a certain hydrogen pressure and a certain reaction temperature; the platinum-containing hybrid nano-structure catalyst is Pt/@ -FeO x SBA-15 catalyst;
the preparation method of the platinum-containing hybrid nano-structure catalyst comprises the following steps: first, feO is precipitated x Coating the film layer on SBA-15Washing, filtering, drying and calcining the molecular sieve to obtain the composite carrier FeO x SBA-15, and anchoring Pt nano particles on composite carrier FeO by photochemical reduction method x and/SBA-15 to obtain the platinum-containing hybrid nano-structure catalyst.
In a specific embodiment, the Pt/@ -FeO x The mass content of Pt in the SBA-15 catalyst is 0.5-2%; the composite carrier FeO x FeO in SBA-15 x The mass content of (2) is 5-20%.
In a specific embodiment, the Pt/@ -FeO x The mass content of Pt in the SBA-15 catalyst is 1.5-2%; the composite carrier FeO x FeO in SBA-15 x The mass content of (2) is 10-15%.
In a specific embodiment, the hydrogen pressure is 0.6-1 MPa, the reaction temperature is 40-60 ℃, and the reaction time for preparing furfuryl alcohol by catalyzing the selective hydrogenation of furfural is 60-100 min.
In a specific embodiment, isopropanol or ethanol is used as the reaction solvent in the selective hydrogenation to produce furfuryl alcohol, preferably isopropanol is used as the reaction solvent.
In a specific embodiment, the preparation method of the platinum-containing hybrid nanostructure catalyst comprises the following specific steps:
step 1, dissolving ferric salt in deionized water, adding a certain amount of SBA-15, and uniformly stirring;
step 2, after ultrasonic stirring, adding an alkali solution to adjust the pH value to 8-9, stirring for 30-90 min at 50-70 ℃, and standing for 2-3 h;
step 3, washing, filtering, drying and calcining the mixed solution obtained in the step 2 to obtain the composite carrier FeO x /SBA-15；
Step 4, the composite carrier FeO prepared in the step 3 x Dissolving SBA-15 in deionized water, adding appropriate amount of anhydrous methanol, ultrasonic dispersing, adding H 2 PtCl 6 Continuing ultrasonic vibration, placing under ultraviolet lamp, stirring at normal temperature overnight, filtering, and washingWashing and vacuum drying to obtain the Pt/@ -FeO x SBA-15 catalyst.
In a specific embodiment, the iron salt in step 1 is ferric nitrate nonahydrate; the alkali solution in the step 2 is sodium carbonate solution, and the concentration of the sodium carbonate solution is 0.2-0.4 mol/L.
In a specific embodiment, the drying temperature in step 3 is 80-100 ℃; the calcination temperature is 400-500 ℃ and the calcination time is 3-4 h.
In a specific embodiment, the ultrasonic oscillation time in the step 4 is 30-60 min; the vacuum drying in the step 4 is performed for 12 hours or more at a temperature of between 70 and 90 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst provided by the invention has excellent catalytic activity when used for catalyzing furfuryl alcohol prepared by selective hydrogenation of furfural, and under mild reaction conditions, the conversion rate and selectivity of furfural can reach 100%. And Pt/@ -FeO used in the invention x The SBA-15 catalyst has simple preparation process, short preparation period and good Pt dispersibility.
2. The invention provides a novel hybridized nano-structure catalyst, which adopts carrier SBA-15 with large specific surface area and ordered regular pore canal, then coats oxide semiconductor film layer on the carrier surface in single layer form, uses Pt nano-particles and FeO x The synergistic effect of the semiconductor film layer produces strong interface electronic effect, so as to greatly raise catalytic performance.
3. The catalyst has simple preparation process, and Pt can be anchored on the molecular sieve with the semiconductor film layer by adopting a photochemical reduction method, and can be prepared by stirring at normal temperature under low-intensity UV irradiation and then vacuum drying δ+ Reduction to Pt 0 The obtained catalyst has good Pt dispersibility.
The catalyst used in the invention is metal Pt nano particles and 2D amorphous semiconductor metal oxide FeO x The Pt hybridized nano-structure catalyst is constructed.
The metal Pt nano particles and the 2D amorphous semiconductor metal oxide are assembled on a carrier with a large specific surface to form a Pt hybridization nano structure catalyst, so that the synergistic catalysis of the metal Pt nano particles and the 2D amorphous semiconductor metal oxide is shown; the strong electron effect at the interface of the metallic Pt nanoparticles and the 2D amorphous semiconductor metal oxide.
The metal oxide loading is controlled in accordance with the spontaneous monolayer dispersion principle to form a 2D amorphous semiconductor metal oxide film (XRD confirmed amorphous, not crystalline) on a large specific surface area support in a monolayer or multiple layers (preferably monolayer). I.e. corresponds to the coating of a metal oxide "gel" on a support with a large specific surface area (e.g. SBA-15), which shows good stability.
The catalyst used in the invention shows the catalytic performance of super high activity; the mild condition can efficiently catalyze the selective hydrogenation of furfural to prepare furfuryl alcohol.
The catalyst used in the invention can catalyze selective hydrogenation reaction with low loading, high activity and high selectivity.
In addition to the objects, features and advantages described above, the present invention has other objects, features and advantages. The present invention will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows Fe according to example 1 of the present invention 2 O 3 、SBA-15、10％FeO x /SBA-15、15％FeO x /SBA-15、20％FeO x SBA-15 and 1.5% Pt/@ -10% FeO x Wide-angle XRD pattern of SBA-15 catalyst
Fig. 2 is a TEM image of example 1 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention, taken in conjunction with the accompanying drawings, is provided to illustrate and not to limit the invention.
Example 1
And (3) preparing a catalyst: 0.5621g of Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 90ml deionized water, adding 1g of carrier SBA-15, stirring uniformly, performing ultrasonic treatment for 30min, and stirring for 1h under the condition of water bath heating at 60 ℃ to uniformly mix; preparation of 0.2mol/L Na 2 CO 3 The pH value of the mixed solution is regulated to 8-9, the mixed solution is continuously stirred for 1h under the water bath heating condition of 60 ℃, the mixed solution is taken out, kept stand and aged for 2h, the obtained solution is washed and filtered by deionized water, dried for 12h at 80 ℃ and calcined for 3h at 400 ℃ to obtain FeO x 10% of composite carrier FeO by mass x SBA-15, i.e. 10% FeO x SBA-15. 0.403g of composite carrier FeO is taken x SBA-15 was dispersed in 40ml deionized water, 6ml absolute methanol was added, sonicated for 30min, and 0.83ml of H containing Pt 0.0074g/ml was added 2 PtCl 6 Continuing ultrasonic oscillation of the solution for 30min, then placing the obtained solution under an ultraviolet lamp, stirring for 12h under illumination, filtering and washing the solution to be neutral, and vacuum drying for 12h at 80 ℃ to obtain 1.5% Pt/@ -10% FeO x SBA-15, i.e. Pt/@ -FeO x The mass content of Pt in the SBA-15 catalyst is 1.5%, and the composite carrier FeO x FeO in SBA-15 x The mass content of (2) was 10%.
Catalyst reaction evaluation: 1.5% Pt/@ -10% FeO x The SBA-15 catalyst is used for catalyzing the selective hydrogenation reaction of furfural. Taking furfural and 1.5 percent Pt/@ -10 percent FeO x Putting SBA-15 catalyst and 20ml isopropanol into a high-pressure reaction kettle, wherein the mol ratio of Pt to furfural is 0.6719%, the hydrogen pressure is set to be 1MPa, the reaction temperature is 60 ℃, after the air in the reaction kettle is replaced by the hydrogen, closing a hydrogen valve, and when the temperature in the kettle reaches the set reaction temperature of 60 ℃, introducing H 2 The stirring is started to react for 100min, and after the reaction is finished, the reaction solution is cooled, and a proper amount of reaction solution is taken for centrifugation and gas chromatography analysis.
Example 2
As in example 1, the difference is Pt/@ -FeO x The mass fraction of Pt in the SBA-15 is 0.5 percent, namely 0.5 percent of Pt/@ -10FeO x /SBA-15。
Example 3
As in example 1, the difference is Pt/@ -FeO x The mass fraction of Pt in the SBA-15 is 1 percent, namely 1 percent of Pt/@ -10FeO x /SBA-15。
Example 4
As in example 1, the difference is Pt/@ -FeO x The mass fraction of Pt in the SBA-15 is 2.0%, namely 2% Pt/@ -10FeO x /SBA-15。
Comparative example 1
As in example 1, the difference is Pt/@ -FeO x The SBA-15 does not contain platinum nano particles, and the mass fraction of Pt is 0, namely 10 percent FeO x /SBA-15。
The results of the catalytic reactions when the catalysts of examples 1 to 4 and comparative example 1 were used for catalyzing the hydrogenation reaction of furfural are shown in Table 1.
TABLE 1 Pt/@ -FeO with different Pt loadings x Results of SBA-15 catalyst catalyzing furfuraldehyde hydrogenation
| Catalyst | Furfural conversion (%) | Furfuryl alcohol selectivity (%) | |
| Example 1 | 1.5％Pt/@-10％FeO x /SBA-15 | 100 | 100 |
| Example 2 | 0.5％Pt/@-10％FeO x /SBA-15 | 39.9 | 100 |
| Example 3 | 1％Pt/@-10％FeO x /SBA-15 | 75.23 | 100 |
| Example 4 | 2％Pt/@-10％FeO x /SBA-15 | 98.91 | 100 |
| Comparative example 1 | 10％FeO x /SBA-15 | 1.57 | 100 |
Table 1 shows that different Pt loadings have little effect on furfuryl alcohol selectivity for furfural hydrogenation, but have a significant effect on furfural conversion. Comparing the results of examples 1 to 4 with the results of comparative example 1, it is clear that the catalyst without supported platinum nanoparticles has lower catalytic activity, and that the catalyst obtains better catalytic activity when a certain amount of platinum nanoparticles are supported. Comparing the results of examples 1 to 3, it was found that when the platinum loading was 0.5%, the conversion of furfural was 39.9% after 100min of reaction at 60 ℃ under 1MPa, and the conversion of furfural gradually increased with increasing platinum loading, indicating that the more active sites on the catalyst, the activated H was in unit time 2 The more the conversion is promoted. Comparing the data from example 1 with example 4 shows that as the platinum loading is further increased, the conversion of furfural is somewhat reduced, indicating that the dispersed platinum particles are just right when the Pt loading is 1.5%Saturation is achieved, and excessive platinum may accumulate in the pores of the carrier, which is detrimental to the full utilization of the platinum, and therefore the Pt/@ -FeO x The mass content of Pt in the SBA-15 catalyst is preferably 1.5 to 2%, more preferably 1.5%.
Example 5
As in example 1, the difference is Pt/@ -FeO x FeO in SBA-15 x Is 5% by mass, i.e. 1.5% Pt/@ -5% FeO x /SBA-15。
Example 6
As in example 1, the difference is Pt/@ -FeO x FeO in SBA-15 x Is 15% by mass, namely 1.5% Pt/@ -15% FeO x /SBA-15。
Example 7
As in example 1, the difference is Pt/@ -FeO x FeO in SBA-15 x Is 20% by mass, namely 1.5% Pt/@ -20% FeO x /SBA-15。
Comparative example 2
As in example 1, the difference is Pt/@ -FeO x FeO in SBA-15 x Is 0, i.e. 1.5% Pt/SBA-15.
In the above examples, feO x The mass fraction of (2) refers to FeO x On a composite carrier FeO x Mass fraction in SBA-15. Pt/@ -FeO in examples 5-7 x The catalytic reaction results of the SBA-15 catalyst used for catalyzing the selective hydrogenation reaction of furfural are shown in Table 2.
TABLE 2 different FeO x Supported Pt/@ -FeO x Results of SBA-15 catalyst catalyzing furfuraldehyde hydrogenation
| Catalyst | Furfural conversion (%) | Furfuryl alcohol selectivity (%) | |
| Example 1 | 1.5％Pt/@-10％FeO x /SBA-15 | 100 | 100 |
| Example 5 | 1.5％Pt/@-5％FeO x /SBA-15 | 87.85 | 100 |
| Example 6 | 1.5％Pt/@-15％FeO x /SBA-15 | 98.65 | 100 |
| Example 7 | 1.5％Pt/@-20％FeO x /SBA-15 | 98.05 | 100 |
| Comparative example 2 | 1.5％Pt/SBA-15 | 1.82 | 100 |
Table 2 shows that different FeOx loadings have little effect on the selectivity of furfural hydrogenation, but have a greater effect on the conversion of furfural. As can be seen from comparison of the data obtained in example 1 and examples 5 to 7, feO x Selection of furfuryl alcohol at 5% loadingThe conversion rate of the furfural can reach 100 percent, but the conversion rate of the furfural does not reach 100 percent, when FeO x When the loading of the furfuraldehyde is increased to 10%, the conversion rate of the furfuraldehyde and the selectivity of the furfuralcohol can reach 100%, and when FeO x As the loading of furfural increases still further, the conversion of furfural decreases somewhat, indicating that theoretically, when FeO x At a loading of 10%, feO x The formed semiconductor film is just a monolayer dispersed on molecular sieve SBA-15, and when the loading increases, it will cause stacking, resulting in a decrease in conversion. As can be seen by comparing the data obtained in examples 1 and 5-7 with the data obtained in comparative example 2, the conversion of furfural was significantly different, indicating FeO x Has great influence on the reaction effect, and confirms that the active components Pt nano particles and FeO x The synergistic effect of the film layers improves the catalytic performance of the catalyst.
Example 8
Example 8 1.5% Pt/@ -10% FeO prepared in example 1 x SBA-15 catalyst, differing in the hydrogenation conditions, specifically the hydrogenation conditions of example 1 are: the reaction temperature is 60 ℃, the hydrogen pressure is 1MPa, and the reaction time is 100min; the hydrogenation conditions for example 8 were: the reaction temperature is 50 ℃, the hydrogen pressure is 1MPa, and the reaction time is 100min.
Example 9
Example 9 1.5% Pt/@ -10% FeO prepared in example 1 x SBA-15 catalyst, differing in the hydrogenation conditions, specifically the hydrogenation conditions of example 1 are: the reaction temperature is 60 ℃, the hydrogen pressure is 1MPa, and the reaction time is 100min; the hydrogenation conditions for example 9 were: the reaction temperature is 40 ℃, the hydrogen pressure is 1MPa, and the reaction time is 100min.
Example 10
Example 10 1.5% Pt/@ -10% FeO prepared in example 1 was used x SBA-15 catalyst, differing in the hydrogenation conditions, specifically the hydrogenation conditions of example 1 are: the reaction temperature is 60 ℃, the hydrogen pressure is 1MPa, and the reaction time is 100min; the hydrogenation conditions for example 10 were: the reaction temperature is 60 ℃, the hydrogen pressure is 0.9MPa, and the reaction is carried outThe time is 100min.
Example 11
Example 11 1.5% Pt/@ -10% FeO prepared in example 1 was used x SBA-15 catalyst, differing in the hydrogenation conditions, specifically the hydrogenation conditions of example 1 are: the reaction temperature is 60 ℃, the hydrogen pressure is 1MPa, and the reaction time is 100min; the hydrogenation conditions for example 11 were: the reaction temperature is 60 ℃, the hydrogen pressure is 1MPa, and the reaction time is 80min.
Example 12
Example 12 1.5% Pt/@ -10% FeO prepared in example 1 was used x SBA-15 catalyst, differing in the hydrogenation conditions, specifically the hydrogenation conditions of example 1 are: the reaction temperature is 60 ℃, the hydrogen pressure is 1MPa, and the reaction time is 100min; the hydrogenation conditions for example 12 were: the reaction temperature is 60 ℃, the hydrogen pressure is 1MPa, and the reaction time is 60min.
TABLE 3 results of Furfural hydrogenation under different hydrogenation reaction conditions
| Temperature (. Degree. C.) | Time (min) | Pressure (MPa) | Furfural conversion (%) | Furfuryl alcohol selectivity (%) | |
| Example 1 | 60 | 100 | 1 | 100 | 100 |
| Example 8 | 50 | 100 | 1 | 93.75 | 100 |
| Example 9 | 40 | 100 | 1 | 62.52 | 100 |
| Example 10 | 60 | 100 | 0.9 | 97.47 | 100 |
| Example 11 | 60 | 80 | 1 | 97.75 | 100 |
| Example 12 | 60 | 60 | 1 | 88.89 | 100 |
As can be seen from Table 3, under the action of the catalyst, any one of the conditions of reaction temperature, pressure and time is changed, the other two conditions are kept unchanged, and the conditions which are more suitable for selective hydrogenation of furfural can be found by comparing with different conditions. Obtaining 1.5 percent Pt/@ -10 percent FeO x The SBA-15 catalyst catalyzes the furfural hydrogenation reaction to achieve 100 percent of furfural conversion rate and 100 percent of furfuryl alcohol selectivity under the conditions of 60 ℃ for 100min, hydrogen pressure of 1MPa and 20mL of isopropanol.
Examples 13A to 13C
As in example 1, except that 1.5% Pt/@ -10% FeO was changed x The SBA-15 catalyst is used as a solvent for catalyzing the hydrogenation reaction of furfural, and the reaction conditions are kept unchanged.
Table 4 results of different media for hydrogenation of furfural
| Solvent(s) | Furfural conversion (%) | Furfuryl alcohol selectivity (%) | |
| Example 1 | Isopropyl alcohol | 100 | 100 |
| Example 13A | Absolute ethyl alcohol | 100 | 99.42 |
| Example 13B | Anhydrous methanol | 31.61 | 100 |
| Example 13C | Water and its preparation method | 28.27 | 100 |
Table 4 shows 1.5% Pt/@ -10% FeO in different reaction media x Influence of SBA-15 catalyst on the selective hydrogenation performance of furfural. As can be seen from the table, when absolute ethyl alcohol is used as a reaction medium, although the conversion rate can reach 100%, the selectivity is slightly different from that of isopropanol, and when absolute methyl alcohol and water are used as reaction media, the catalytic effect of furfural hydrogenation is not ideal, so that the catalytic effect of isopropanol is optimal.
From the above examples, the catalysts with different mass fractions provided by the invention are active for selective hydrogenation of furfural, and most of the catalysts can achieve excellent catalytic activity on the premise of adjusting and changing the catalytic reaction temperature, hydrogen pressure and reaction time. The scope of the invention is not limited to the above examples, and good effects on the hydrogenation reaction of furfural can be achieved as long as the mass fraction of the active components of the catalyst and the reaction conditions are controlled.
The foregoing is a further detailed description of the invention in connection with specific preferred embodiments, and is not intended to limit the practice of the invention to such description. It will be apparent to those skilled in the art that several simple deductions and substitutions can be made without departing from the spirit of the invention, and these are considered to be within the scope of the invention.
Claims (5)
1. A method for preparing furfuryl alcohol by hydrogenation of furfural is characterized by comprising the steps of using a platinum-containing hybrid nano-structure catalyst, and catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol under the conditions of a reaction solvent, a certain hydrogen pressure and a certain reaction temperature; the platinum-containing hybrid nano-structure catalyst is Pt/@ -FeO x SBA-15 catalyst;
the preparation method of the platinum-containing hybrid nano-structure catalyst comprises the following steps: first, feO is precipitated x Coating a membrane layer on the SBA-15 molecular sieve, washing, filtering, drying and calcining to obtain the composite carrier FeO x SBA-15, and anchoring Pt nano particles on composite carrier FeO by photochemical reduction method x On SBA-15, obtaining the platinum-containing hybrid nano-structure catalyst;
the Pt/@ -FeO x The mass content of Pt in the SBA-15 catalyst is 1.5-2%; the composite carrier FeO x FeO in SBA-15 x The mass content of (2) is 10-15%;
the hydrogen pressure is 0.6-1 MPa, the reaction temperature is 40-60 ℃, and the reaction time for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural is 60-100 min; isopropyl alcohol or ethanol is used as a reaction solvent in the reaction for preparing furfuryl alcohol by selective hydrogenation;
the preparation method of the platinum-containing hybrid nano-structure catalyst comprises the following specific steps:
step 1, dissolving ferric salt in deionized water, adding a certain amount of SBA-15, and uniformly stirring;
step 2, after ultrasonic stirring, adding an alkali solution to adjust the pH value to 8-9, stirring for 30-90 min at 50-70 ℃, and standing for 2-3 h;
step 3, washing, filtering, drying and calcining the mixed solution obtained in the step 2 to obtain the composite carrier FeO x /SBA-15；
Step 4, the composite carrier FeO prepared in the step 3 x Dissolving SBA-15 in deionized water, adding appropriate amount of anhydrous methanol, ultrasonic dispersing, adding H 2 PtCl 6 Continuing ultrasonic oscillation of the solution, then placing under an ultraviolet lamp, stirring overnight at normal temperature, filtering, washing and vacuum drying the obtained solution to obtain the Pt/@ -FeO x SBA-15 catalyst.
2. The method for preparing furfuryl alcohol by hydrogenating furfural according to claim 1, wherein isopropanol is used as a reaction solvent in the reaction for preparing furfuryl alcohol by selective hydrogenation.
3. The method for preparing furfuryl alcohol by hydrogenating furfural according to claim 1, wherein the ferric salt in step 1 is ferric nitrate nonahydrate; the alkali solution in the step 2 is sodium carbonate solution, and the concentration of the sodium carbonate solution is 0.2-0.4 mol/L.
4. The method for preparing furfuryl alcohol by hydrogenating furfural according to claim 1, wherein the drying temperature in the step 3 is 80-100 ℃; the calcination temperature is 400-500 ℃ and the calcination time is 3-4 h.
5. The method for preparing furfuryl alcohol by hydrogenating furfural according to claim 1, wherein the ultrasonic oscillation time in the step 4 is 30-60 min; the vacuum drying in the step 4 is performed for 12 hours or more at a temperature of between 70 and 90 ℃.
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| CN109529912A (en) * | 2018-12-28 | 2019-03-29 | 湘潭大学 | Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof |
| CN110193370A (en) * | 2019-04-23 | 2019-09-03 | 江西理工大学 | The bimetallic catalyst and preparation method, application of furfural selective hydrogenation furfuryl alcohol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109529912A (en) * | 2018-12-28 | 2019-03-29 | 湘潭大学 | Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof |
| CN110193370A (en) * | 2019-04-23 | 2019-09-03 | 江西理工大学 | The bimetallic catalyst and preparation method, application of furfural selective hydrogenation furfuryl alcohol |
Non-Patent Citations (3)
| Title |
|---|
| Efficient Cu/FeOx catalyst with developed structure for catalytic transfer hydrogenation of furfural;J. Luo, Y. Cheng, H. Niu et al.;《Journal of Catalysis》;第413卷;第575–587页 * |
| Qiaoyun Liu, et al.Catalytic production of 1,4-pentanediol from furfural in a fixed-bed system under mild conditions .《Green Chem》.2020,第22卷第3532–3538页. * |
| Selective hydrogenation of cinnamaldehyde with PtFex/Al2O3@SBA-15 catalyst: Enhancement in activity and selectivity to unsaturated alcohol by Pt-FeOx and Pt-Al2O3@SBA-15 interaction;H. Pan et al.;《Journal of Catalysis》;第354卷;第24–36页 * |
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