CN108059594B - Method for converting biomass monomer into clean fuel by green synthesis of Pd catalyst - Google Patents
Method for converting biomass monomer into clean fuel by green synthesis of Pd catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002028 Biomass Substances 0.000 title claims abstract description 12
- 239000000446 fuel Substances 0.000 title claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 238000003786 synthesis reaction Methods 0.000 title claims description 6
- 239000000178 monomer Substances 0.000 title claims description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 188
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 81
- 230000003197 catalytic effect Effects 0.000 claims abstract description 53
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229940040102 levulinic acid Drugs 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 83
- 238000003756 stirring Methods 0.000 claims description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 20
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical group CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012876 carrier material Substances 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012696 Pd precursors Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- YNUJADNRNHJXDT-UHFFFAOYSA-N palladium;pentane-2,4-dione Chemical group [Pd].CC(=O)CC(C)=O.CC(=O)CC(C)=O YNUJADNRNHJXDT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 239000012847 fine chemical Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 49
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 48
- 239000000047 product Substances 0.000 description 39
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 24
- 239000000706 filtrate Substances 0.000 description 18
- 238000004817 gas chromatography Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 229940005605 valeric acid Drugs 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 17
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 13
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 13
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 11
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 11
- 239000002551 biofuel Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
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- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CSKRBHOAJUMOKJ-UHFFFAOYSA-N 3,4-diacetylhexane-2,5-dione Chemical compound CC(=O)C(C(C)=O)C(C(C)=O)C(C)=O CSKRBHOAJUMOKJ-UHFFFAOYSA-N 0.000 description 1
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
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- 238000007210 heterogeneous catalysis Methods 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- FGPPDYNPZTUNIU-UHFFFAOYSA-N pentyl pentanoate Chemical compound CCCCCOC(=O)CCCC FGPPDYNPZTUNIU-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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Abstract
The invention discloses a method for selectively preparing clean fuel and fine chemicals by controlling and synthesizing a Pd-based catalyst by a green Chemical Fluid Deposition (CFD) method and catalyzing a biomass platform compound, which comprises the following steps: putting the supported nano Pd catalyst and levulinic acid or furfural into a reaction kettle filled with a solvent, introducing hydrogen (20-100 bar) under the protection of inert gas, and reacting for 6-20 hours at 150-270 ℃. The catalytic system provided by the invention has the following characteristics: (1) adopting green solvent CO2The improved CFD method has mild reaction conditions and effectively prevents Pd particles from agglomerating and losing; (2) the prepared metal Pd catalyst shows excellent catalytic performance and high selectivity; (3) the metal consumption is low (1-7 wt%); (4) the acid sites on the carrier and the metal active center generate synergistic action, and (5) the catalyst has good stability, and the efficiency is not obviously reduced after the circulation for many times.
Description
Technical Field
The invention belongs to the field of clean fuel development by an environment-friendly catalysis technology, and particularly relates to a method for selectively preparing clean fuel and high-value fine chemicals by synthesizing a Pd-based catalyst and catalyzing a biomass platform compound by a green CFD (circulating fluid bed) method.
Background
With the gradual depletion of global fossil resources, the rapid increase of energy demand, and the close attention of people to environmental problems, the development of biofuel production using renewable biomass resources and fine chemicals having high values have received extensive attention and research. Furfural is a very attractive platform molecule compound for the production of biofuels and high value added chemicals, such as Furfural (FA), tetrahydrofurfuryl alcohol (THFA), Tetrahydrofuran (THF), furan, 2-Methylfuran (MF) and 2-Methyltetrahydrofuran (MTHF). Among them, furfural is an important organic chemical product and widely used in the industries of synthetic plastics, dyes, medicines, pesticides, and the like. Tetrahydrofurfuryl alcohol, another high value-added compound, contains 31.3 wt% of oxygen and is generally used as an environment-friendly raw material for producing products such as pesticides, paints, dyes and the like. Tetrahydrofurfuryl alcohol has recently been extensively studied as a clean fuel. However, in order to achieve the purpose of efficiently producing furfuryl alcohol and tetrahydrofurfuryl alcohol, a large amount of toxic and harmful chemical reagents are needed, so that the production cost is increased, the ecological environment is polluted, and the concept of sustainable development is violated. Therefore, the development of an environmentally friendly preparation method is urgently needed.
Levulinic Acid (LA) is widely used to produce various commercial chemicals, such as fine chemicals pentanoic acid (VA) and biofuel Gamma Valerolactone (GVL), 2-Methyltetrahydrofuran (MTHF), ethyl levulinate, etc., which can be obtained from a variety of cellulose-containing environmental wastes by a cost-effective method. Among these valuable chemicals, gamma valerolactone is an ideal renewable green platform compound that can be used not only as a liquid fuel by itself but also for the preparation of carbon-based consumables. Valeric acid, which has unique properties, has been widely used as another important fine chemical for the preparation of biofuels, such as ethyl valerate and amyl valerate. Furthermore, valeric acid, which has a high energy density, is also considered as a raw material for sustainable production of transportation fuels. Efficient production of pentanoic acid is becoming increasingly important and most pentanoic acid is produced by reacting gamma valerolactone as a starting material.
Although many methods have made great progress in the research on the catalytic conversion of levulinic acid to gamma valerolactone, the direct conversion to pentanoic acid is less, and some challenging problems still exist, such as (1) organic waste is often generated by organic solvents used in the synthesis process of the commonly used catalyst in the literature report, which has serious impact on the environment; (2) the size of the synthesized metal nano-particles is difficult to control, and the metal nano-particles are easy to agglomerate on the surface of a carrier material and are easy to run off in the reaction process; (3) the synthesis steps of valeric acid are complex or gamma-valerolactone is directly used as a raw material; (4) the catalytic product is difficult to control and has low selectivity. Therefore, how to realize the high-selectivity one-step hydrogenation of levulinic acid to prepare gamma-valerolactone and pentanoic acid and make the catalytic system environment-friendly, high in catalytic activity, mild in reaction condition, strong in circulation stability and low in cost becomes a problem to be solved urgently in the research field.
Disclosure of Invention
The invention mainly aims to provide a method for selectively preparing clean fuel and fine chemicals by synthesizing a Pd-based catalyst and catalyzing a biomass platform compound by a green CFD method. The method can realize (1) one-step high-efficiency catalytic selective preparation of gamma-valerolactone and valeric acid from levulinic acid; (2) selectively preparing furfuryl alcohol and tetrahydrofurfuryl alcohol by efficiently hydrogenating and catalyzing furfural; (3) providing an environmentally friendly CO2The improved CFD method for synthesizing the bifunctional catalyst system (with an acid site and a metal active center) can be recycled for many times, and the catalytic performance is stable, so that the method is more environment-friendly, the overall preparation cost is reduced, and the industrial production is favorably realized.
The invention provides a method for selectively preparing clean fuel and fine chemicals by synthesizing a Pd-based catalyst and catalyzing a biomass platform compound by a green CFD (circulating fluid bed) method, which specifically comprises the following steps:
(1) dispersing a biomass platform compound and a Pd catalyst in a reaction solvent according to a certain proportion in a glass reactor arranged in a reaction kettle, and then filling inert gas into the reaction solvent to ensure that the reaction solvent is in vacuum;
(2) filling hydrogen into the reactor, controlling the pressure of the reactor to be within the range of 20-100 bar by a pressure gauge, continuously reacting for 6-20 hours after the temperature of the catalytic system reaches 150-270 ℃, and continuously stirring in the whole reaction process at the stirring speed of 900-2000 rpm;
(3) after the reaction is finished, the reaction kettle is cooled to room temperature, and a target reaction product is obtained through filtration and separation.
The Pd catalyst system consists of a carrier material and Pd loaded on the carrier material, and is prepared by using a green solvent CO2The improved Chemical Fluid Deposition (CFD) method is prepared by the following specific steps:
(1) adding 200-300 mg of carrier material and a certain amount of Pd precursor into a 50mL Parr reactor, then sealing the reactor and introducing 12-20 g of CO2；
(2) Continuously stirring the mixture obtained in the step (1) for 12-24 hours at room temperature to ensure that the Pd precursor is completely dispersed in the solution;
(3) after the reaction is finished, decompressing the reactor, cooling to room temperature, calcining the sample obtained in the step (2) at the temperature of 60-450 ℃ for 1-5 hours, and raising the temperature at the speed of 2-5 ℃/min;
(4) using liquid CO for the sample obtained in the step (3)2Pressurizing, stirring for 6-12 hours at room temperature, rotating at 1000-3500 rpm, and introducing H2And (4) reducing.
The carrier material of the Pd catalyst is MCM-41, AlMCM-41, ZrMCM-4, TiMCM-41, SnMCM-41, gamma-Al2O3And multi-walled Carbon Nanotubes (CNTs).
The precursor of Pd in the Pd catalyst is bis (acetylacetone) palladium (II) (Pd (acac)2) Palladium (II) acetate (Pd (OAc)2) And (allyl) (cyclopentadienyl) palladium (Pd (allyl) Cp).
The load amount of Pd in the Pd catalyst is 1-7 wt%.
The biomass platform compound is one of levulinic acid or furfural.
The mass ratio of the Pd catalyst to the levulinic acid is 1: 30-1: 50.
The mass ratio of the Pd catalyst to the furfural is 1: 23-1: 46.
The reaction solvent is octane or deionized water, and the inert gas is nitrogen or argon.
Compared with the prior art, the invention has the following beneficial effects:
1. the synthesized metal Pd catalyst has excellent catalytic activity and selectivity, the conversion rate of levulinic acid exceeds 99 percent, and the selectivity of gamma valerolactone and valeric acid can reach 88.5 percent and 45.1 percent respectively; the conversion rate of the furfural can reach 54.7 percent, and the selectivity of the furfuryl alcohol and the tetrahydrofurfuryl alcohol can reach 54.8 percent and 32.3 percent respectively.
2. The catalytic system is applied to the preparation of biofuel gamma-valerolactone (50.6 percent of selectivity) and fine chemical valeric acid (45.1 percent of selectivity) by one-step hydrogenation of levulinic acid, the raw material levulinic acid can be completely converted after the reaction is finished, and the catalytic system is suitable for the reaction with water as a solvent, so that the use of an organic solvent is avoided.
3. The result of applying the catalytic system to furfural hydrogenation catalysis shows that the selectivity of furfuryl alcohol and tetrahydrofurfuryl alcohol exceeds 87% under mild reaction conditions.
4. The reaction condition is relatively mild, the reaction temperature and pressure are lower than those of the traditional heterogeneous catalyst, and the whole reaction process does not need to use a large amount of inorganic acid or alkali, so that the safety of a catalytic system is improved, and the generated waste liquid is prevented from polluting the environment.
5. The used bifunctional heterogeneous catalysis system has an acid site and a metal active center, can generate a synergistic effect, and avoids the use of additional chemical agents.
6. By using green CO2The low-temperature control synthesis by the CFD method is improved, so that the adverse effect on the environment can be reduced, the Pd particles are fixed in the mesoporous channels of the molecular sieve, the Pd particle agglomeration is effectively prevented, and the loss of active metal in the reaction process is reduced.
7. The used load metal Pd is low (1-7 wt%), and the cost of the catalyst is reduced on the whole.
8. The catalyst has good catalytic stability, the efficiency is not obviously reduced after the catalyst is circulated for many times, a complex regeneration process is not needed, and the catalyst has higher industrial application value.
Drawings
FIG. 1 is a TEM analysis of a nano Pd catalyst prepared by the present invention; wherein (a)5 wt% Pd/MCM-41; (b)5 wt% Pd/AlMCM-41; (c)5 wt% Pd/ZrMCM-41;
FIG. 2 is an XRD pattern of a 5 wt% Pd/MCM-41 catalyst prepared according to the invention.
Detailed Description
The invention will be further elucidated by means of the following figures and examples, without the scope of protection of the invention being limited to the ones shown.
Example 1:
preparation of Pd-supported catalyst:
0.2g MCM-41 and 10mg palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, which was then charged with 12g CO2And sealing. The above mixed solution was stirred continuously at room temperature for 24 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm. The TEM pattern and XRD pattern of the obtained 5 wt% Pd/MCM-41 are shown in FIG. 1(a) and FIG. 2, respectively.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.3g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled by a pressure gauge at 60 bar. When the temperature of the catalytic system reaches 240 ℃, the reaction is continued for 10 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is 56.7 percent, and the selectivity of the gamma valerolactone and the valeric acid is 46.9 percent and 0.2 percent.
Example 2:
preparation of Pd-supported catalyst:
0.2g MCM-41 and 14mg palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, which was then charged with 12g CO2And sealing. The mixed solution is continuously stirred for 24 hours at room temperature to ensure that the palladium (I) bis (acetylacetone)I) Highly dispersed in solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.3g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled by a pressure gauge at 60 bar. When the temperature of the catalytic system reaches 240 ℃, the reaction is continued for 10 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is 53.9 percent, and the selectivity of the gamma valerolactone and the valeric acid is 47.3 percent and 0.3 percent.
Example 3:
preparation of Pd-supported catalyst:
0.2g of AlMCM-41 and 10mg of bis (acetylacetonato) palladium (II) were charged into a 50mL reaction vessel, which was then charged with 12g of CO2And sealing. The above mixed solution was stirred continuously at room temperature for 24 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm. The TEM spectrum of the resulting 5 wt% Pd/AlMCM-41 is shown in FIG. 1 (b).
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.3g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled by a pressure gauge at 60 bar. When the temperature of the catalytic system reaches 240 ℃, the reaction is continued for 10 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is more than 99 percent, and the selectivity of the gamma valerolactone and the valeric acid is 88.5 percent and 9.7 percent.
Example 4:
preparation of Pd-supported catalyst:
0.2g ZrMCM-41 and 10mg palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, which was then charged with 12g CO2And sealing. The above mixed solution was stirred continuously at room temperature for 24 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm. The TEM spectrum of the obtained 5 wt% Pd/ZrMCM-41 is shown in FIG. 1 (c).
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.3g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled by a pressure gauge at 60 bar. When the temperature of the catalytic system reaches 240 ℃, the reaction is continued for 10 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is 77.2 percent, and the selectivity of the gamma valerolactone and the valeric acid is 72.3 percent and 2.9 percent.
Example 5:
preparation of Pd-supported catalyst:
0.2g of SnMCM-41 and 10mg of palladium (II) acetate were charged into a 50mL reaction vessel, which was then charged with 14gCO2And sealing. Continuously stirring the mixed solution at room temperature for 20 hours to ensure that the palladium (II) acetate is high in the solutionAnd (4) degree dispersion. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 5 hours at 400 ℃ in an air environment, and the heating rate is 3 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.3g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled by a pressure gauge at 100 bar. And (3) continuously reacting for 20 hours after the temperature of the catalytic system reaches 230 ℃, and continuously stirring in the whole reaction process at the stirring speed of 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is more than 99 percent, and the selectivity of the gamma valerolactone and the valeric acid is 73.7 percent and 22.4 percent.
Example 6:
preparation of Pd-supported catalyst:
0.2g of TiMCM-41 and 10mg of (allyl) (cyclopentadienyl) palladium were charged into a 50mL reaction vessel, which was then charged with 14g of CO2And sealing. The above mixed solution was stirred at room temperature for 20 hours to ensure that the (allyl) (cyclopentadienyl) palladium was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 5 hours at 400 ℃ in an air environment, and the heating rate is 3 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.3g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled at 40bar by a pressure gauge. And (3) continuously reacting for 20 hours after the temperature of the catalytic system reaches 230 ℃, and continuously stirring in the whole reaction process at the stirring speed of 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is more than 99 percent, and the selectivity of the gamma valerolactone and the valeric acid is 88.0 percent and 10.5 percent.
Example 7:
preparation of Pd-supported catalyst:
0.2g of AlMCM-41 and 10mg of palladium (II) acetate were charged into a 50mL reaction vessel, which was then charged with 14gCO2And sealing. The above mixed solution was stirred continuously at room temperature for 20 hours to ensure that the palladium (II) acetate was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.3g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled at 40bar by a pressure gauge. When the temperature of the catalytic system reaches 230 ℃, the reaction is continued for 10 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is 39.7 percent, and the selectivity of the gamma valerolactone and the valeric acid is 34.1 percent and 0.4 percent.
Example 8:
preparation of Pd-supported catalyst:
0.2g of TiMCM-41 and 10mg of palladium (II) acetate were charged into a 50mL reaction vessel, which was then charged with 14gCO2And sealing. The above mixed solution was stirred continuously at room temperature for 20 hours to ensure that the palladium (II) acetate was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 5 hours at 400 ℃ in an air environment, and the heating rate is 3 ℃/min. Finally obtainTo the sample with liquid CO2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.5g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen gas and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled at 40bar by a pressure gauge. When the temperature of the catalytic system reaches 270 ℃, the reaction is continued for 10 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is 88.9 percent, and the selectivity of the gamma valerolactone and the valeric acid is 68.2 percent and 19.6 percent.
After 4 times of continuous circulation experiments, the conversion rate of the regenerated bifunctional Pd catalytic system for catalyzing the levulinic acid is still as high as 85.9%, and the selectivity of gamma valerolactone and pentanoic acid is respectively 62.7% and 21.4%. In addition, ICP analysis indicated no loss of active metal Pd to the reaction solution (Pd (< 5ppm)), further demonstrating the green CO provided by the present invention2The improved CFD method can firmly fix Pd particles in the pore channels of the mesoporous molecular sieve, and prevent the Pd particles from agglomerating and losing in the reaction process.
Example 9:
preparation of Pd-supported catalyst:
0.2g of SnMCM-41 and 10mg of (allyl) (cyclopentadienyl) palladium were charged into a 50mL reaction vessel, which was then charged with 14g of CO2And sealing. The above mixed solution was stirred at room temperature for 20 hours to ensure that the (allyl) (cyclopentadienyl) palladium was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 5 hours at 400 ℃ in an air environment, and the heating rate is 3 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.5g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen gas and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled by a pressure gauge at 100 bar. When the temperature of the catalytic system reaches 230 ℃, the reaction is continued for 10 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is more than 99 percent, and the selectivity of the gamma valerolactone and the valeric acid is 82.9 percent and 16.0 percent.
Example 10:
preparation of Pd-supported catalyst:
0.2g of AlMCM-41 and 10mg of (allyl) (cyclopentadienyl) palladium were charged into a 50mL reaction vessel, which was then charged with 14g of CO2And sealing. The above mixed solution was stirred at room temperature for 20 hours to ensure that the (allyl) (cyclopentadienyl) palladium was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 3 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.3g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled by a pressure gauge at 100 bar. When the temperature of the catalytic system reaches 270 ℃, the reaction is continued for 10 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is more than 99 percent, and the selectivity of the gamma valerolactone and the valeric acid is 50.6 percent and 45.1 percent.
Example 11:
preparation of Pd-supported catalyst:
0.2g of AlMCM-41 and 10mg of bis (acetylacetonato) palladium (II) were charged into a 50mL reaction vessel, which was then charged with 12g of CO2And sealing. The above mixed solution was stirred continuously at room temperature for 24 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1500 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and placed in a reaction vessel, 0.3g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of an octane solvent, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled by a pressure gauge at 100 bar. And when the temperature of the catalytic system reaches 270 ℃, the reaction is continued for 20 hours, and the stirring is continuously carried out in the whole reaction process, wherein the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is more than 99 percent, and the selectivity of the gamma valerolactone and the valeric acid is 49.1 percent and 40.9 percent.
Example 12:
preparation of Pd-supported catalyst:
0.3g γ-Al2O3and 15mg of palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, which was then charged with 18g of CO2And sealing. The above mixed solution was stirred continuously at room temperature for 24 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 5 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 2000 rpm.
And (3) testing the catalytic performance:
in a glass reactor with 25mL in a reaction vessel, 5.0g of levulinic acid and 0.1g of supported nano Pd catalyst were dispersed in 5mL of deionized water, followed by argon gas injection and vacuum. Thereafter, the reactor was filled with hydrogen and the pressure was controlled at 45bar by a pressure gauge. When the temperature of the catalytic system reaches 160 ℃, the reaction is continued for 6 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is 63.2 percent, and the selectivity of the gamma valerolactone and the valeric acid is 96.3 percent and 3.7 percent.
Example 13:
preparation of Pd-supported catalyst:
0.3g CNT and 15mg palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, which was then charged with 18gCO2And sealing. The above mixed solution was stirred continuously at room temperature for 12 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 1 hour at 80 ℃ in an air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 6 hours at a stirring speed of 3500 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL in a reaction vessel, 3.0g of levulinic acid and 0.1g of a supported nano Pd catalyst were dispersed in 5mL of deionized water, followed by introduction of nitrogen and vacuum-pumping. Thereafter, the reactor was filled with hydrogen and the pressure was controlled by a pressure gauge at 60 bar. When the temperature of the catalytic system reaches 200 ℃, the reaction is continued for 8 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the levulinic acid is 57.6 percent and the selectivity of the gamma valerolactone is 56.3 percent.
Example 14:
preparation of Pd-supported catalyst:
0.2g MCM-41 and 10mg palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, followed by reactionThe reactor was charged with 20g of CO2And sealing. The above mixed solution was stirred continuously at room temperature for 20 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at the temperature of 60 ℃ in the air environment, and the heating rate is 3 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 10 hours at a stirring speed of 2500rpm, maintaining the pressure at 20 bar.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL in a reaction vessel, 2.0mL of furfural and 0.1g of supported nano-Pd catalyst were dispersed in 5mL of octane solution, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled at 45bar by a pressure gauge. When the temperature of the catalytic system reaches 160 ℃, the reaction is continued for 6 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 900 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the furfural is 45.3 percent, and the selectivity of the furfuryl alcohol and the tetrahydrofurfuryl alcohol is 60.3 percent and 28.9 percent.
Example 15:
preparation of Pd-supported catalyst:
0.2g MCM-41 and 14mg palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, which was then charged with 20g CO2And sealing. The above mixed solution was stirred continuously at room temperature for 20 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at the temperature of 60 ℃ in the air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 10 hours at a stirring speed of 2500rpm, maintaining the pressure at 20 bar.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL in a reaction vessel, 2.0mL of furfural and 0.1g of supported nano-Pd catalyst were dispersed in 5mL of octane solution, followed by introduction of nitrogen and vacuum evacuation. Thereafter, the reactor was filled with hydrogen and the pressure was controlled at 45bar by a pressure gauge. When the temperature of the catalytic system reaches 160 ℃, the reaction is continued for 6 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography, wherein the conversion rate of the furfural is 54.7%, and the selectivity of the furfuryl alcohol and the tetrahydrofurfuryl alcohol is 54.8% and 32.3% respectively.
Example 16:
preparation of Pd-supported catalyst:
0.3g γ-Al2O3and 3mg of palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, which was then charged with 18g of CO2And sealing. The above mixed solution was stirred continuously at room temperature for 24 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 4 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL in a reaction vessel, 3.0mL of furfural and 0.1g of supported nano-Pd catalyst were dispersed in 5mL of octane solution, followed by introduction of argon gas and vacuum-pumping. Thereafter, the reactor was filled with hydrogen and the pressure was controlled at 45bar by a pressure gauge. When the temperature of the catalytic system reaches 150 ℃, the reaction is continued for 6 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the furfural is 21.2 percent, and the selectivity of the furfuryl alcohol and the tetrahydrofurfuryl alcohol is 90.3 percent and 6.5 percent.
Example 17:
preparation of Pd-supported catalyst:
0.3g γ-Al2O3and 9mg of palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, which was then charged with 18g of CO2And sealing. Mixing the above materialsThe solution was stirred continuously at room temperature for 18 hours to ensure that the palladium (II) bis (acetylacetonate) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and built in a reaction vessel, 4.0mL of furfural and 0.1g of supported nano-Pd catalyst were dispersed in 5mL of octane solution, followed by introduction of argon and vacuum-pumping. Thereafter, the reactor was filled with hydrogen and the pressure was controlled at 80bar by a pressure gauge. When the temperature of the catalytic system reaches 150 ℃, the reaction is continued for 6 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 1500 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the furfural is 26.9 percent, and the selectivity of the furfuryl alcohol and the tetrahydrofurfuryl alcohol is 89.1 percent and 7.6 percent.
Example 18:
preparation of Pd-supported catalyst:
0.3g γ-Al2O3and 15mg of palladium (II) bis (acetylacetonate) were charged into a 50mL reaction vessel, which was then charged with 18g of CO2And sealing. The above mixed solution was stirred continuously at room temperature for 16 hours to ensure that the bis (acetylacetonato) palladium (II) was highly dispersed in the solution. After the reaction is finished, the pressure of the reaction kettle is reduced, the obtained sample is calcined for 3 hours at 450 ℃ in an air environment, and the heating rate is 2 ℃/min. Finally obtaining liquid CO for sample2And H2The reduction was carried out at room temperature for 12 hours at a stirring speed of 1000 rpm.
And (3) testing the catalytic performance:
in a glass reactor having a capacity of 25mL and built in a reaction vessel, 4.0mL of furfural and 0.1g of supported nano-Pd catalyst were dispersed in 5mL of octane solution, followed by introduction of argon and vacuum-pumping. Thereafter, the reactor was filled with hydrogen and the pressure was controlled at 20bar by a pressure gauge. When the temperature of the catalytic system reaches 150 ℃, the reaction is continued for 6 hours, the stirring is continuously carried out in the whole reaction process, and the stirring speed is 2000 rpm. After the reaction is finished, cooling the reaction kettle to room temperature, filtering and separating the product from the catalyst, treating the filtrate, and analyzing the product by using gas chromatography to respectively calculate that the conversion rate of the furfural is 39.4 percent, and the selectivity of the furfuryl alcohol and the tetrahydrofurfuryl alcohol is 84.9 percent and 13.8 percent.
Claims (5)
1. A method for converting biomass monomer into clean fuel by using a green Pd synthesis catalyst is characterized by comprising the following steps:
(1) dispersing a biomass platform compound and a Pd catalyst in a reaction solvent according to a certain proportion in a glass reactor arranged in a reaction kettle, and then filling inert gas into the reaction solvent to ensure that the reaction solvent is in vacuum;
(2) filling hydrogen into the reactor, controlling the pressure of the reactor to be within the range of 20-100 bar by a pressure gauge, continuously reacting for 6-20 hours after the temperature of the catalytic system reaches 150-270 ℃, and continuously stirring in the whole reaction process at the stirring speed of 900-2000 rpm;
(3) after the reaction is finished, cooling the reaction kettle to room temperature, and filtering and separating to obtain a target reaction product;
the Pd catalyst consists of a carrier material and Pd supported on the carrier material, and is prepared by using a green solvent CO2The improved Chemical Fluid Deposition (CFD) method is prepared by the following specific steps:
(1) adding 200-300 mg of carrier material and a certain amount of Pd precursor into a 50mL Parr reactor, then sealing the reactor and introducing 12-20 g of CO2；
(2) Continuously stirring the mixture obtained in the step (1) for 12-24 hours at room temperature to ensure that the Pd precursor is completely dispersed in the solution;
(3) after the reaction is finished, decompressing the reactor, cooling to room temperature, calcining the sample obtained in the step (2) at the temperature of 60-450 ℃ for 1-5 hours, and raising the temperature at the speed of 2-5 ℃/min;
(4) using liquid CO for the sample obtained in the step (3)2Pressurizing, stirring for 6-12 hours at room temperature with the rotation speed of 1000-3500 rpm, and introducing H2Reduction ofObtaining the Pd catalyst;
the carrier material of the Pd catalyst is MCM-41, AlMCM-41, ZrMCM-41, TiMCM-41, SnMCM-41, gamma-Al2O3And multi-walled carbon nanotubes;
the precursor of Pd in the Pd catalyst is bis (acetylacetone) palladium (II) (Pd (acac)2) Palladium (II) acetate (Pd (OAc)2) And (allyl) (cyclopentadienyl) palladium (Pd (allyl) Cp);
the load amount of Pd in the Pd catalyst is 1-7 wt%.
2. The method of claim 1, wherein the biomass platform compound is one of levulinic acid or furfural.
3. The method according to claim 2, wherein the mass ratio of the Pd catalyst to the levulinic acid is 1: 30 to 1: 50.
4. The method according to claim 2, wherein the mass ratio of the Pd catalyst to the furfural is 1: 23-1: 46.
5. The method of claim 1, wherein the reaction solvent is octane or deionized water and the inert gas is nitrogen or argon.
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