CN110227473B - Method for catalytically synthesizing gamma-valerolactone by using short nano rod-shaped solid acid - Google Patents
Method for catalytically synthesizing gamma-valerolactone by using short nano rod-shaped solid acid Download PDFInfo
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000011973 solid acid Substances 0.000 title claims abstract description 34
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229940040102 levulinic acid Drugs 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000002274 desiccant Substances 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000002073 nanorod Substances 0.000 abstract description 7
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 229910052759 nickel Inorganic materials 0.000 description 23
- 239000002028 Biomass Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- 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 short rod-shaped solid acid catalyst Ni @ ZrO2‑CeO2Method for catalytically synthesizing gamma-valerolactone from ZrO2‑CeO2As a carrier, Ni2O is impregnated and roasted and loaded on ZrO2‑CeO2On a carrier, in H2The acid active sites obtained by the lower reduction are dispersed uniformly, have stable structure and are difficult to be Ni2O corrosion collapsed short nano rod-shaped structure solid acid catalyst Ni @ ZrO2‑CeO2The length of the nano-rod is 21-31 nm, the diameter is 8-12 nm, and the specific surface area is 62-94 m2The acid content is 1.11-1.52 mmol/g, the catalyst is suitable for catalyzing levulinic acid hydrogenation reaction to synthesize gamma-valerolactone, the mass ratio of the catalyst to the levulinic acid is 0.29:1, the mass ratio of the levulinic acid to methanol is 0.11:1, the reaction temperature is 180 ℃, the reaction time is 6 hours, and the yield of the gamma-valerolactone reaches 98%.
Description
Technical Field
The invention belongs to the field of biomass energy catalysis, and relates to a short nano rod-shaped solid acid Ni @ ZrO2-CeO2A method for catalytically synthesizing gamma-valerolactone.
Background
The biomass energy is renewable energy, and the biomass conversion can be carried out by organisms,Pyrolysis, enzymatic or chemical routes, where the chemical process has a wide range of raw material sources. Gamma valerolactone is a renewable energy source converted from the hydrogenation reaction of a biomass-based platform compound, levulinic acid. It can be used as resin solvent and intermediate of various related compounds, and also can be used as lubricant, plasticizer, gelling agent of nonionic surfactant and lactone additive of leaded gasoline, and can be used for dyeing cellulose ester and synthetic fibre. The gamma-valerolactone also has the fragrance of vanillin and coconut, and is an edible spice which is allowed to be used in the specification of GB2760-86 in China, and is mainly used for preparing essences of peach type, coconut type, vanilla type and the like, and also used as a solvent of insoluble resin and an organic synthesis intermediate. The invention prepares short rod-shaped solid acid Ni @ ZrO2-CeO2CeO after doping with Zr2Soaking Ni-loaded in lower alcohol solvent at low temperature for stabilizing mixed metal oxide carrier, roasting in air atmosphere, and reducing in hydrogen atmosphere to obtain short nanorod-shaped solid acid catalyst Ni @ ZrO with stable structure2-CeO2The gamma-valerolactone is prepared by catalyzing levulinic acid to be hydrogenated, and the mass yield of the gamma-valerolactone reaches 98 percent.
Disclosure of Invention
Objects of the invention
The invention aims to provide a short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2A method for catalytically synthesizing gamma-valerolactone.
Technical scheme of the invention
1. Short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2The method is characterized in that:
the short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2In, Ni and carrier ZrO2-CeO2The mass ratio of (A) to (B) is 0.12-0.33: 1;
the ZrO2-CeO2The molar ratio of Zr to Ce in the carrier is 0.1-0.3: 1;
the short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2In the formula, Ni is a component for enhancing acidity, and the acid content is 1.11-1.52 mmol/g;
the short nano rod-shaped solid acidCatalyst Ni @ ZrO2-CeO2Has a length of 21 to 31nm, a diameter of 8 to 12nm, and a specific surface area of 62 to 94m2/g。
2. Preparation of the short nanorod-shaped solid acid catalyst Ni @ ZrO 12-CeO2The method is characterized in that: firstly, CeO which has certain acidity, more active physical and chemical properties, less stable structure and volatile electron removal is used2ZrO with rich doped surface defects2Forming stable short nano rod-shaped ZrO by hydrothermal crystallization and roasting2-CeO2The carrier is impregnated with Ni and then roasted to obtain the short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2The method comprises the following steps:
zr (NO)3)4·5H2O and Ce (NO)3)3·6H2Dissolving O in deionized water according to a molar ratio of 0.1-0.3: 1 to form a solution A with a total molar concentration of 0.1-0.15 mol/L, dissolving NaOH in deionized water to form a solution B with a total molar concentration of 10-12.5 mol/L, slowly adding the solution B into the solution A under stirring, stirring and mixing for 20-40 min at 40-45 ℃ to form a mixed sol, transferring the mixed sol into a polytetrafluoroethylene lining for crystallization for 24-36 h at 90-100 ℃, cooling to room temperature to form a precipitate, performing suction filtration, washing a filter cake to be neutral by using a mixed solution with an ethanol-water mass ratio of 0.5-1: 1, drying at a constant temperature of 80-100 ℃ for 10-12 h, placing in a box-type muffle furnace, raising the temperature to 400-600 ℃ at a rate of 1.5-3 ℃/min, roasting for 4-6 h, and cooling to obtain the ZrO2-CeO2A carrier;
mixing Ni (NO)3)2·6H2O, ZrO prepared above2-CeO2Adding a carrier and an impregnant into a beaker according to a mass ratio of 0.59-0.93: 1: 17-23, impregnating and stirring for 4-6 h at 40-60 ℃, heating to 55-70 ℃, evaporating and recovering the impregnant, drying the residual light green powdery solid at a constant temperature of 80-100 ℃ for 10-12 h, placing the dried solid in a box-type muffle furnace at a heating rate of 1.5-3 ℃/min to 400-450 ℃ for roasting for 4-6 h, then heating to 450-500 ℃ at a heating rate of 2-5 ℃/min in a tubular furnace, reducing for 1-2 h in a hydrogen atmosphere,after cooling, the short rod-shaped solid acid catalyst Ni @ ZrO is prepared2-CeO2The drying agent can be effectively kept in a dryer for 7-14 days, and is not required to be reduced before use;
the impregnant is absolute methanol or absolute ethanol;
the reduction is to load ZrO2-CeO2NiO of (2)2Reducing the Ni into simple substance as a catalytic active site.
3. The short nano rod-shaped solid acid catalyst Ni @ ZrO of 12-CeO2The method for catalyzing levulinic acid to synthesize gamma valerolactone is characterized by comprising the following steps of: the mass ratio of the raw material levulinic acid to methanol is 0.05-0.11: 1, and the short nano rod-shaped solid acid catalyst Ni/ZrO2-CeO2Reacting the methyl levulinate and the levulinic acid at the mass ratio of 0.22-0.29: 1, the pressure of introduced hydrogen gas of 2.8-3.2 MPa and the reaction temperature of 180-220 ℃ for 4-6 h, reacting the levulinic acid with methanol to generate methyl levulinate, and then using a catalyst Ni @ ZrO2-CeO2Catalyzing methyl levulinate to hydrogenate under the action to generate gamma-valerolactone, cooling to room temperature after the reaction is finished, evaporating methanol after centrifugally separating a lower-layer catalyst to obtain relatively pure gamma-valerolactone, wherein the yield of the gamma-valerolactone product reaches 98%, precipitating and filtering the centrifugally separated lower-layer catalyst, washing a filter cake for 3 times by using anhydrous methanol, drying the filter cake for 10-12 hours in a constant-temperature drying box at the temperature of 80-100 ℃, raising the temperature to 400-600 ℃ at the heating rate of 1.5-3 ℃/min, roasting for 4-6 hours, reducing for 1-2 hours at the temperature of 450-500 ℃ under the hydrogen atmosphere, and using the catalyst for repeated use next time.
Technical features and effects of the invention
1. Firstly preparing ZrO of short nanorod structure carrier2-CeO2Soaking Ni in methanol or ethanol, and calcining at 450 deg.C in air to obtain short nanorod solid acid catalyst Ni @ ZrO with uniformly distributed and stable acid active sites2-CeO2。
2. Due to ZrO2Large specific surface area and abundant surface defects, Ni2+Can enter ZrO2Lattice and substitution of part of Zr4+And due to Ni2+Has electronegativity less than Zr4+Thus making Zr4+AmbientO of (A) to (B)2-The electron cloud density is further improved, the acid strength is enhanced, the electron cloud is a Lewis acid site, and methyl levulinate is catalyzed on metal Ni to be hydrogenated to generate gamma-valerolactone.
3. The solid acid catalyst is easy to separate from the product, has good catalytic performance and high catalytic efficiency, is suitable for catalyzing levulinic acid hydrogenation reaction to generate gamma-valerolactone, and is a short nanorod solid acid catalyst Ni @ ZrO2-CeO2The mass ratio of the gamma-valerolactone to the levulinic acid is 0.2-0.4: 1, the reaction temperature is 180-220 ℃, the reaction time is 4-6 h, the hydrogen pressure is 2-3.4 MPa, and the yield of the gamma-valerolactone reaches 98%.
Drawings
FIG. 1 shows a solid acid catalyst carrier ZrO of short nanorods2-CeO2And short nanorod solid acid catalyst Ni @ ZrO2-CeO2Transmission Electron Microscopy (TEM) image of the sample, wherein (a) and (b) are ZrO with a resolution of 20nm, respectively2-CeO 210% Ni @ ZrO-loaded with 10% Ni by mass2-CeO2TEM image of (a), (c) Ni catalyst 10% Ni @ ZrO at a resolution of 50nm with a loading mass percentage of 10%2-CeO2A TEM image of (a). From (a), ZrO2-CeO2Is short nano rod-like structure with insufficient dispersibility, NiO is loaded after soaking in anhydrous methanol, and after roasting, the short nano rod-like structure is maintained at all times from (b) and (c), but the diameter is increased, and the dispersibility is improved because of ZrO2-CeO2The surface of the carrier is loaded with Ni.
FIG. 2 shows different Ni loading masses Ni @ ZrO2-CeO2A high angle XRD pattern of the sample wherein (a) is ZrO2-CeO2The Ni loading mass percentages of the catalyst carrier (b), (c), (d), (e) and (f) are 5%, 10%, 15%, 20% and 30% of Ni @ ZrO respectively2-CeO2Large angle XRD pattern of (a). (b) Diffraction peaks corresponding to (c), (d), (e) and (f) at 43.2 degrees represent Ni (111) plane, diffraction peaks at 37.1 degrees and 62.8 degrees represent NiO (111) and NiO (220) plane respectively, and diffraction peaks at 28.7 degrees, 33.0 degrees, 47.4 degrees, 56.5 degrees, 59.1 degrees, 69.4 degrees, 76.6 degrees and 79.3 degrees are attributed to CeO2(111), (200), (220), (31) of face centered cubic structure (JCPDS)1) (222), (400), (331), and (420). In all catalysts, ZrO2There was no significant diffraction peak, indicating that Zr ions were doped into CeO2In the structure, form ZrO2-CeO2Solid solution of Ni at 43.2 degree and NiO at 37.1 degree and 62.8 degree with increasing Ni load2The diffraction peak becomes gradually sharper, which shows that Ni is well loaded on the carrier ZrO2-CeO2The above.
FIG. 3 is 10% Ni @ ZrO2-CeO2XPS chart of (a). XPS analysis to find Ni @ CeO2-ZrO2The valence state of the metal present in the sample. In the graph a, XPS signals with binding energies of 882.62eV, 853.43eV, and 182.13eV correspond to characteristic peaks of Ce, Ni, and Zr, respectively. In FIG. b, a high resolution scan of Ni2p shows the presence of energy level peaks for 2p3/2 elemental nickel and Ni2p1/2 nickel oxide at 853.4eV and 871.8eV, respectively. Panel c shows that the XPS signal at binding energy 882.62eV is a characteristic peak for metal Ce. The Zr3d binding energy peak in FIG. d appears at 182.13eV, indicating that zirconium is present as ZrO in the solid acid2The C, O peak appearing in pattern a is due to surface oxidation of the sample during analytical transfer.
FIG. 4 shows the distribution of acid sites on the surface of a solid acid consisting of NH3Determination of TPD, finding Ni @ ZrO2-CeO2NH of (2)3The desorption curve shows mainly 4 signals, the peak below 250 ℃ being attributed to weak acids and the peak in the range of 250 ℃ and 450 ℃ to medium strong acids. The acid sites play a decisive role in the reaction of hydrogenation of levulinic acid to gamma valerolactone.
FIG. 5 is Ni @ ZrO2-CeO2H of catalyst2TPR plot, H of solid acid2Two reduction peaks occur in the TPR: the peak at 250 ℃ is considered to be a trace of trivalent nickel, the peak around 450 ℃ is considered to be nickel oxide which has a weak interaction with the catalyst support, indicating that the nickel oxide is converted to the simple substance of nickel upon reduction at 500 ℃, and the absence of other peaks indicates that the support ZrO is supported2-CeO2Are not reduced.
Detailed Description
The technical means and the mode of carrying out the present invention will be described below by way of examples, but the technical means and the mode of carrying out the present invention are not limited to the following examples.
Example 1
1.Ni@ZrO2-CeO2Preparation of
Zr (NO)3)4·5H2O、Ce(NO3)3·6H2Dissolving O in deionized water according to the molar ratio of 1:9 to form a solution A with the total molar concentration of 0.125mol/L, slowly adding NaOH solution with the molar concentration of 12mol/L into the solution A under the stirring state, stirring for 30min at 40 ℃, transferring the formed mixed sol into a reaction kettle with a polytetrafluoroethylene lining for crystallization for 24h at 100 ℃, cooling to room temperature, performing suction filtration on the formed precipitate, washing the precipitate to be neutral by using a mixed solution with the mass ratio of alcohol to water of 1:1, drying the filter cake at the constant temperature of 100 ℃ for 12h, placing the filter cake into a box-type muffle furnace, heating to 400 ℃ at the heating rate of 2 ℃/min, roasting for 5h, and cooling to obtain the ZrO with the short nano rod-like structure2-CeO2The length of the short nanorods is 50-55 nm, the diameter is 7-9 nm, and the specific surface area is 100-110 m2/g。
Then adding Ni (NO)3)2·6H2O, short nano rod-shaped structure ZrO prepared2-CeO2Adding a carrier and an impregnant anhydrous methanol into a polytetrafluoroethylene beaker according to a mass ratio of 0.5:1:20, soaking and stirring for 6h at 40 ℃, heating to 60 ℃, evaporating the impregnant, drying the rest obtained light yellow powdery solid for 12h at a constant temperature of 100 ℃, placing the dried light yellow powdery solid into a box-type muffle furnace, heating to 400 ℃ at a heating rate of 2 ℃/min, roasting for 5h, cooling, and reducing for 60min in a tubular furnace at 500 ℃ before use to obtain 10% Ni @ ZrO2-CeO2Catalyst of (2), i.e. Ni represents Ni @ ZrO2-CeO210% of the total mass.
2.10％Ni@ZrO2-CeO2Catalytic hydrogenation synthesis of gamma-valerolactone
Levulinic acid, absolute methanol and the prepared 10 percent Ni @ ZrO2-CeO2Adding solid acid into polytetrafluoroethylene lining of a reaction kettle, wherein the mass ratio of levulinic acid to methanol is 0.09:1, the mass ratio of catalyst to levulinic acid is 0.29:1, and introducing pressure of 2.8MPaHydrogen at the reaction temperature of 180 ℃ for 6h, cooling to room temperature after the reaction is finished, centrifuging for the second time to separate reaction liquid and a catalyst to obtain the gamma-valerolactone with the mass yield of 98%, precipitating and filtering the centrifuged lower-layer solid acid, washing a filter cake for 3 times by using absolute methanol, drying in a constant-temperature drying box at the temperature of 100 ℃ for 12h, raising the temperature to 400 ℃ at the rate of 2 ℃/min, and roasting for 5h to be used as the catalyst for the next time for repeated use.
Example 2 the procedure of example 1 was followed except that the hydrogen pressure was 2MPa, the reaction temperature was 120 ℃ and the catalyst was 5% Ni @ ZrO 22-CeO2The mass yield of the gamma-valerolactone is 13 percent.
Example 3 the procedure of example 1 was followed except that the hydrogen pressure was 2MPa, the reaction temperature was 120 ℃ and the catalyst was 10% Ni @ ZrO2-CeO2The mass yield of the gamma-valerolactone is 42 percent.
Example 4 the procedure of example 1 was followed except that the hydrogen pressure was 2MPa, the reaction temperature was 120 ℃ and the catalyst was 15% Ni @ ZrO2-CeO2The mass yield of the gamma-valerolactone is 38 percent.
Example 5 the procedure of example 1 was followed except that the hydrogen pressure was 2MPa, the reaction temperature was 120 ℃ and the catalyst was 20% Ni @ ZrO2-CeO2The mass yield of the gamma-valerolactone is 37 percent.
EXAMPLE 6 the procedure of example 1 was followed except that the hydrogen pressure was 2MPa, the reaction temperature was 120 ℃ and the catalyst was 30% Ni @ ZrO2-CeO2The mass yield of the gamma-valerolactone is 37 percent.
Example 7 the procedure of example 1 was followed, except that the hydrogen pressure was 2MPa and the reaction temperature was 140 ℃ to give 38% gamma-valerolactone mass yield.
Example 8 the procedure of example 1 was followed, except that the hydrogen pressure was 2MPa and the reaction temperature was 160 deg.C, giving a gamma-valerolactone mass yield of 54%.
Example 9 the procedure of example 1 was followed, except that the hydrogen pressure was 2MPa and the reaction temperature was 180 ℃ to obtain a gamma-valerolactone mass yield of 86%.
Example 10 the procedure of example 1 was followed, except that the hydrogen pressure was 2MPa and the reaction temperature was 200 ℃ to give a gamma-valerolactone mass yield of 70%.
EXAMPLE 11 the procedure of example 1 was followed, except that the hydrogen pressure was 2MPa and the reaction temperature was 220 ℃ to obtain a gamma-valerolactone mass yield of 74%.
EXAMPLE 12 the procedure of example 1 was followed, except that the hydrogen pressure was 2.4MPa, whereby the gamma-valerolactone mass yield was 79%.
EXAMPLE 13 the procedure of example 1 was followed, except that the hydrogen pressure was 3.0MPa, and the mass yield of gamma-valerolactone was 92%.
EXAMPLE 14 the procedure of example 1 was followed, except that the hydrogen pressure was 3.2MPa, and the mass yield of gamma-valerolactone was 90%.
EXAMPLE 15 the procedure of example 1 was followed, except that the hydrogen pressure was 3.4MPa, and the mass yield of gamma-valerolactone was 82%.
Example 16 the procedure of example 1 was followed, but the reaction time was 2 hours, giving a gamma-valerolactone mass yield of 59%.
Example 17 the procedure of example 1 was followed, but the reaction time was 3 hours, giving a mass yield of 66% gamma-valerolactone.
EXAMPLE 18 the procedure of example 1 was followed, except that the reaction time was 4 hours, to obtain gamma-valerolactone in a mass yield of 75%.
EXAMPLE 19 the procedure of example 1 was followed, except that the reaction time was 5 hours, to obtain gamma-valerolactone in a mass yield of 83%.
EXAMPLE 20 the procedure of example 1 was followed except that the catalyst was 10% Ni @ ZrO2-CeO2The roasting temperature is 250 ℃, and the yield of the gamma-valerolactone mass ester is 60 percent.
EXAMPLE 21 the procedure of example 1 was followed except that the catalyst was 10% Ni @ ZrO2-CeO2The roasting temperature is 350 ℃, and the mass yield of the gamma-valerolactone is 71 percent.
EXAMPLE 22 the procedure of example 1 was followed except that the catalyst was 10% Ni @ ZrO2-CeO2The roasting temperature is 550 ℃, and the mass yield of the gamma-valerolactone is 66%.
EXAMPLE 23 the procedure of example 1 was followed except that the catalyst was 10% Ni @ ZrO2-CeO2The roasting temperature is 650 ℃ to obtain the gamma-pentaneThe lactone mass yield was 79%.
EXAMPLE 24 the procedure of example 1 was followed except that the catalyst was 10% Ni @ ZrO2-CeO2The mass ratio of the gamma-valerolactone to the levulinic acid is 0.15:1, and the mass yield of the gamma-valerolactone is 80 percent.
EXAMPLE 25 the procedure of example 1 was followed except that the catalyst was 10% Ni @ ZrO2-CeO2The mass ratio of the gamma-valerolactone to the levulinic acid is 0.17:1, and the mass yield of the gamma-valerolactone is 85 percent.
EXAMPLE 26 the procedure of example 1 was followed except that the catalyst was 10% Ni @ ZrO2-CeO2The mass ratio of the gamma-valerolactone to the levulinic acid is 0.22:1, and the mass yield of the gamma-valerolactone is 92 percent.
EXAMPLE 27 the procedure of example 1 was followed except that the catalyst was 10% Ni @ ZrO2-CeO2The mass ratio of the gamma-valerolactone to the levulinic acid is 0.28:1, and the mass yield of the gamma-valerolactone is 93 percent.
TABLE 1 operating conditions and reaction results for examples 1-23
Claims (1)
1. Short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2The method for catalyzing levulinic acid to synthesize gamma valerolactone is characterized by comprising the following steps of:
the mass ratio of the raw material levulinic acid to methanol is 0.05-0.11: 1, and the short nano rod-shaped solid acid catalyst Ni/ZrO2-CeO2Reacting the solution with levulinic acid for 6 hours at the mass ratio of 0.29:1, the introduced hydrogen pressure of 2.8MPa and the reaction temperature of 180 ℃, reacting the levulinic acid with methanol to generate methyl levulinate, and then performing Ni @ ZrO catalysis on the methyl levulinate2-CeO2Catalyzing methyl levulinate to hydrogenate under the action to generate gamma-valerolactone, cooling to room temperature after the reaction is finished, evaporating methanol after centrifugally separating a lower-layer catalyst to obtain relatively pure gamma-valerolactone, wherein the yield of the gamma-valerolactone product reaches 98%, precipitating and filtering the centrifugally separated lower-layer catalyst, washing a filter cake for 3 times by using anhydrous methanol, drying the filter cake for 10-12 hours in a constant-temperature drying box at the temperature of 80-100 ℃, raising the temperature to 400-600 ℃ at the heating rate of 1.5-3 ℃/min, roasting for 4-6 hours, reducing for 1-2 hours at the temperature of 450-500 ℃ in a hydrogen atmosphere, and using the catalyst for the next time for repeated use;
short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2In, Ni and carrier ZrO2-CeO2The mass ratio of (A) to (B) is 0.12-0.33: 1; ZrO (ZrO)2-CeO2The molar ratio of Zr to Ce in the carrier is 0.1-0.3: 1; short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2In the formula, Ni is a component for enhancing acidity, and the acid content is 1.11-1.52 mmol/g; short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2Has a length of 21 to 31nm, a diameter of 8 to 12nm, and a specific surface area of 62 to 94m2/g；
Short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2Is prepared by the following method: firstly, CeO which has certain acidity, more active physical and chemical properties, less stable structure and volatile electron removal is used2ZrO with rich doped surface defects2Forming stable short nano rod-shaped ZrO by hydrothermal crystallization and roasting2-CeO2The carrier is impregnated with Ni and then roasted to obtain the short nano rod-shaped solid acid catalyst Ni @ ZrO2-CeO2The method comprises the following steps: zr (NO)3)4·5H2O and Ce (NO)3)3·6H2Dissolving O in deionized water according to a molar ratio of 0.1-0.3: 1 to form a solution A with a total molar concentration of 0.1-0.15 mol/L, dissolving NaOH in deionized water to form a solution B with a concentration of 10-12.5 mol/L, slowly adding the solution B into the solution A under stirring, stirring and mixing at 40-45 ℃ for 20-40 min to form a mixed sol, transferring the mixed sol into a polytetrafluoroethylene lining, crystallizing at 90-100 ℃ for 24-36 h, cooling to room temperatureForming a precipitate, performing suction filtration, washing a filter cake to be neutral by using a mixed solution of ethanol and water in a mass ratio of 0.5-1: 1, drying at a constant temperature of 80-100 ℃ for 10-12 h, placing in a box-type muffle furnace, raising the temperature to 400-600 ℃ at a heating rate of 1.5-3 ℃/min, roasting for 4-6 h, and cooling to obtain ZrO2-CeO2A carrier; mixing Ni (NO)3)2·6H2O、ZrO2-CeO2Adding a carrier and an impregnant into a beaker according to a mass ratio of 0.59-0.93: 1: 17-23, impregnating and stirring for 4-6 h at 40-60 ℃, heating to 55-70 ℃, evaporating and recovering the impregnant, drying the residual light green powdery solid at a constant temperature of 80-100 ℃ for 10-12 h, placing the dried solid in a box-type muffle furnace at a heating rate of 1.5-3 ℃/min to 450 ℃ for roasting for 4-6 h, then heating to 450-500 ℃ at a heating rate of 2-5 ℃/min in a tube furnace, reducing for 1-2 h in a hydrogen atmosphere, and cooling to obtain the short rod-shaped solid acid catalyst Ni ZrO 22-CeO2The drying agent can be effectively kept in a dryer for 7-14 days, and is not required to be reduced before use; the impregnant is absolute methanol or absolute ethanol; the reduction is to load ZrO2-CeO2NiO of (2)2Reducing the Ni into simple substance as a catalytic active site.
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