CN110229045B - Method for efficiently hydrogenating and converting furfuryl alcohol and high-dispersion supported Pt catalyst - Google Patents
Method for efficiently hydrogenating and converting furfuryl alcohol and high-dispersion supported Pt catalyst Download PDFInfo
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000006185 dispersion Substances 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims abstract description 14
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 14
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 14
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 14
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000002309 gasification Methods 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002028 Biomass Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000012495 reaction gas Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 20
- 229910052593 corundum Inorganic materials 0.000 description 20
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 239000012685 metal catalyst precursor Substances 0.000 description 8
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 7
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 7
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 6
- 102000020897 Formins Human genes 0.000 description 5
- 108091022623 Formins Proteins 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003430 antimalarial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
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- C—CHEMISTRY; METALLURGY
- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
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- C—CHEMISTRY; METALLURGY
- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for efficiently hydrogenating and converting furfuryl alcohol and a high-dispersion supported Pt catalyst belong to the field of biomass catalytic conversion. Adopts a high-dispersion load type Pt catalyst, and belongs to the field of biomass catalytic conversion. On-line on a miniature fixed bed reaction device at a certain H2Under the pressure and the reaction temperature, furfuryl alcohol enters the gasification chamber of the device through a liquid pressure pump and is uniformly mixed with reaction gas hydrogen to enter the reactor. The Pt-containing metal catalyst is composed of a Pt metal active center which is uniformly dispersed and a composite oxide obtained by calcining hydrotalcite, and the active center of the catalyst is a Pt monoatomic and Pt atomic cluster which is highly dispersed in the atomic level. The invention has the advantages that the reaction can be continuously and stably operated for a long time, and Pt in the catalyst and the carrier form strong interaction. On monoatomic Pt, the conversion rate of furfuryl alcohol is 87%, and the selectivity of 2-methylfuran reaches 93%. On atomic cluster Pt, the conversion rate of furfuryl alcohol is 100%, and the selectivity of 1, 2-pentanediol reaches 86%.
Description
Technical Field
The invention belongs to the technical field of biomass catalytic conversion, and particularly provides a method for efficiently hydrogenating and converting furfuryl alcohol and a high-dispersion supported Pt catalyst.
Background
Biomass resources have the characteristics of wide distribution, abundant reserves, renewability and the like, and the production of fuels and fine chemicals from biomass and platform molecules thereof gradually draws wide attention. Furfural (FFA) is one of the most important platform molecules in biomass, and is considered to be one of the most important chemicals for lignocellulosic biomass production. Currently, furfural production is mainly achieved by acid catalysis of pentosan in biomass feedstocks. Furfuryl Alcohol (FA), obtained by hydrogenation of furfural C ═ O bonds, is one of the most important chemicals from furfural hydrogenation products. It is estimated that 62% of furfural produced annually worldwide is converted to furfuryl alcohol. The furfural/furfuryl alcohol can be used for producing a series of fine chemicals with high added values through hydrogenation reaction. Selective hydrogenation and hydrogenolysis are considered to be the most efficient methods for converting furan compounds into valuable chemicals. Furfural/furfuryl alcohol can be converted to various fuel components and fine chemicals by selective hydrogenation. For example: when the C-O bond on the side chain of the FA/FFA furan ring is hydrogenolysed, the product is 2-methylfuran (2-MF). 2-MF is a colorless liquid which is flammable and insoluble in water, and can be used as a solvent and a raw material for producing antimalarial drugs, pesticides, methyltetrahydrofuran, and perfume intermediates. Hydrogenation of two C ═ C on the FA/FFA furan ring can yield tetrahydrofurfuryl alcohol (THFA). It is a water-soluble furan chemical that can be used as a solvent for fats and resins. Tetrahydrofurfuryl alcohol is also known as an environmentally friendly solvent, is less toxic and easily degraded in nature, and is widely used in various fields in industry. Selective hydrogenolysis of the C-O bond on the furan ring of FA/FFA leads to the formation of 1, 2-pentanediol and 1, 5-pentanediol. 1, 2-pentanediol (1,2-PeD) is a water-soluble polyol with antibacterial activity, and can be used as antiseptic in cosmetics and disinfectants. In addition, it can be used as a polyester monomer having an ester functional group in the main chain. Such polyesters have a wide range of applications, such as textiles, packaging materials and engineering plastics. 1, 5-pentanediol (1,5-PeD) is an important chemical intermediate and is widely used in various fields of chemical industry, such as polyurethane, polyester, plasticization and fragrance. All these components have their own important applications in industry, but their synthesis under green reaction conditions is a major challenge.
Due to the diversity of chemical bonds (C ═ C, C-O-H and C ═ O) in biomass and its platform molecules, there are often competing or continuous reaction processes in the reaction, and the selective activation and directional conversion of specific chemical bonds are a great challenge, and there is a problem of low selectivity of target products. The catalyst structure is effectively controlled in the process of converting biomass platform molecule hydrogenation into high value-added chemicals. However, controlling the synthesis of metal catalysts with high activity and high selectivity to the target product remains a difficult point. The size, shape, electronic structure and the like of the metal catalyst can be changed to regulate and control the electronic structure and geometric structure of the active site. The hydrogenation performance of the catalyst can be obviously improved by controlling the structure of the metal catalyst.
Disclosure of Invention
The invention aims to provide a method for efficiently hydrogenating and converting furfuryl alcohol and a high-dispersion supported Pt catalyst.
In order to realize the purpose, the method is carried out on a miniature fixed bed reaction device, the catalyst is a Pt-containing catalyst, the reaction pressure is 0-3 MPa and is not 0, and the ethanol solution of furfuryl alcohol enters a gasification chamber of the device through a liquid pressure pump and reacts with a gas H2Uniformly mixing the mixture and entering a reactor, wherein the reaction temperature is 160-300 ℃. Furfuryl alcohol and H are preferred2In a proportion of 1/100 mol.
The catalyst is used for catalyzing furfuryl alcohol hydrogenation reaction to prepare 1, 2-pentanediol.
The Pt-containing catalyst comprises a Pt metal active center and a composite oxide obtained by calcining hydrotalcite, wherein the Pt metal active center is uniformly dispersed, the content of the Pt metal active center in the catalyst is preferably 0.08-1.67 wt%, and the Pt metal active center is a single atom or an atomic cluster (the particle size is 0.9-1.6 nm).
Preparation of Pt-containing catalyst: the double metal composite hydroxide is also called hydrotalcite (LDHs for short) as carrier, and the divalent cation of hydrotalcite laminate is Mg2+The trivalent cation is Al3+. Growing hydrotalcite in situ on gamma-Al by in-situ growth method2O3A surface. Prepared hydrotalcite carrier impregnated Pt2+Solution to be impregnated with Pt2+The precursor of the post hydrotalcite sample is in H2Reducing in atmosphere at 300-400 deg.C for 60-120min to obtain Pt-containing catalyst, such as Pt/Mg (Al) O-IR. To obtain a monoatomic Pt metal active center in H2Calcining in air before reduction at 400 ℃ at 300 ℃ for 60-120 min.
The invention has the following advantages:
1. the catalyst consists of evenly dispersed metal active center platinum and carrier magnesium aluminum composite oxide. The atomic-level high-dispersion Pt catalyst is prepared in situ by utilizing the atomic-level even dispersion of hydrotalcite slab elements and the crystal lattice induction effect.
2. The catalytic performance can be kept stable for a long time, and the reaction activity and the product selectivity can quickly reach a stable value after the reaction.
3. The preparation method of the supported Pt catalyst is simple and is beneficial to being applied to the industrial production process.
4. The invention can lead the conversion rate of the furfuryl alcohol to reach 100 percent and lead the selectivity of the product 1, 2-pentanediol to be higher.
On monoatomic Pt, the conversion rate of furfuryl alcohol is 87%, and the selectivity of 2-methylfuran reaches 93%. On atomic cluster Pt, the conversion rate of furfuryl alcohol is 100%, and the selectivity of 1, 2-pentanediol reaches 86%.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
The Pt catalyst is applied to the reaction process of preparing high value-added chemicals by catalyzing furfuryl alcohol conversion. The reaction conditions were as follows: evaluation of catalytic performance of the supported Pt catalyst the catalyst was evaluated on a microtube catalyst evaluation apparatus, and the reaction tube was designed to have an inner diameter d of 10mm and a length l of 380 mm. The evaluation apparatus comprises two gas feed lines, typically H, and a liquid feed line2And N2The liquid feed line pumps the liquid reactant into the apparatus via a pressure pump. High temperature conditions are required in view of the catalyst evaluation reaction, with the presence of H2And flammable and explosive substances such as ethanol and the like, so that pressure building and leakage testing must be carried out before each tubulation evaluation reaction, and the good air tightness of the device is ensured without air leakage and liquid leakage.
Example 1
Step A: MgAl-LDHs is grown in situ on gamma-Al by using an in-situ growth method2O3A surface. First, 11mmol Mg (NO) was added to 5.5mL deionized water3)2·6H2Dissolving O and 33mmol of urea to prepare Mg2+-a urea solution. Then, will be configuredIs poured into the solution already filled with gamma-Al2O3Pellets (5g) were placed in a 15ml autoclave and then placed in a shaker and shaken for 1 h. Finally, crystallizing in an oven at 120 ℃ for 12 hours. After crystallization is finished, the obtained solid is washed by deionized water for many times until the solid is neutral. Drying was carried out at 60 ℃ overnight. To prepare MgAl-LDHs @ Al2O3。
And B: adopting an incipient wetness impregnation method to prepare MgAl-LDHs @ Al2O3Upper load of Pt2+. Will [ Pt (NH)3)4](NO3)2Dissolved in deionized water. Dropwise adding the uniformly mixed solution into the prepared MgAl-LDHs @ Al2O3A10 ml flask was then placed in a shaker and shaken for 1 h. Drying at 60 ℃ overnight to give Pt2+Theoretical loading of 0.10% of Pt respectively2 +/MgAl-LDHs@Al2O3And (3) precursor.
The precursor obtained above was used in a microtube catalyst evaluation apparatus, and 1g of a Pt metal catalyst precursor was weighed and charged into a thermocouple and a reaction tube, and the remaining part was filled with quartz sand. Firstly, the catalyst is reduced in situ on line, air is introduced, and the volume space velocity is set to be in the air atmosphere (40mL min)-1) And raising the temperature to 400 ℃ for 2h at 5 ℃ for min. Switching to N2And (4) purging. After the temperature is reduced to 300 ℃, the temperature is switched to H2And preserving the temperature for 1h to obtain the Pt monatomic catalyst. After the temperature of the reaction tube is reduced to 200 ℃, the pressure of the whole device is increased to 3MPa through a back pressure valve. An ethanol solution of furfuryl alcohol was pumped at 100. mu.l.min by a liquid feed pump-1Injecting into a reactor, opening a circulating condensing device, collecting liquid products in a gas-liquid separation tank, and sampling once every 1 h. The catalytic product is analyzed on line by gas chromatography, and the conversion rate of furfuryl alcohol is 87% and the selectivity of 2-methylfuran is 93% under the stable reaction state are measured.
Example 2
Step A: MgAl-LDHs is grown in situ on gamma-Al by using an in-situ growth method2O3A surface. First, 11mmol Mg (NO) was added to 5.5mL deionized water3)2·6H2O and 33mmol of urea solutionSolution to Mg2+-a urea solution. Then, the prepared solution is poured into the solution filled with the gamma-Al2O3Pellets (5g) were placed in a 15ml autoclave and then placed in a shaker and shaken for 1 h. Finally, crystallizing in an oven at 120 ℃ for 12 hours. After crystallization is finished, the obtained solid is washed by deionized water for many times until the solid is neutral. Drying was carried out at 60 ℃ overnight. To prepare MgAl-LDHs @ Al2O3
And B: adopting an incipient wetness impregnation method to prepare MgAl-LDHs @ Al2O3Upper load of Pt2+. Firstly, the [ Pt (NH)3)4](NO3)2Dissolved in deionized water. Dropwise adding the uniformly mixed solution into the prepared MgAl-LDHs @ Al2O3A10 ml flask was then placed in a shaker and shaken for 1 h. Drying at 60 ℃ overnight to give Pt2+Theoretical loading of 1.80% of Pt respectively2+/MgAl-LDHs@Al2O3。
The Pt metal catalyst precursor of example 2 was used on a microtubular catalyst evaluation unit. 1g of Pt metal catalyst precursor was weighed, charged into a thermocouple well in the reaction tube, and the remaining part was filled with quartz sand. Firstly, the catalyst is reduced in situ on line, and reducing gas H is introduced2The volume space velocity is set to be H2Under atmosphere (40mL min)-1) And raising the temperature to 400 ℃ for 2h at 5 ℃ for min. The average size of Pt metal centers is about 1.6nm atom clusters. After the temperature of the reaction tube is reduced to 200 ℃, the pressure of the whole device is increased to 3MPa through a back pressure valve, then the temperature of the preheating box is increased to 160 ℃, and the temperature of the pipeline heat-preservation heating belt is increased to 140 ℃. An ethanol solution of furfuryl alcohol was pumped at 100. mu.l.min by a liquid feed pump-1Injecting into a reactor, opening a circulating condensing device, collecting liquid products in a gas-liquid separation tank, and sampling once every 1 h. The catalytic product is analyzed on line by gas chromatography, and the conversion rate of furfuryl alcohol is 100% and the selectivity of 1, 2-pentanediol is 86% under the stable reaction state are measured. The selectivity of tetrahydrofurfuryl alcohol is 6 percent.
Comparative example 2
Step A: MgAl-LDHs is grown in situ on gamma-Al by using an in-situ growth method2O3A surface. First, 11mmol Mg (NO) was added to 5.5mL deionized water3)2·6H2Dissolving O and 33mmol of urea to prepare Mg2+-a urea solution. Then, the prepared solution is poured into the solution filled with the gamma-Al2O3Pellets (5g) were placed in a 15ml autoclave and then placed in a shaker and shaken for 1 h. Finally, crystallizing in an oven at 120 ℃ for 12 hours. After crystallization is finished, the obtained solid is washed by deionized water for many times until the solid is neutral. Drying was carried out at 60 ℃ overnight. To prepare MgAl-LDHs @ Al2O3。
And B: adopting an incipient wetness impregnation method to prepare MgAl-LDHs @ Al2O3Upper load of Pt2+. Firstly, the [ Pt (NH)3)4](NO3)2Dissolved in deionized water. Dropwise adding the uniformly mixed solution into the prepared MgAl-LDHs @ Al2O3A10 ml flask was then placed in a shaker and shaken for 1 h. Drying at 60 ℃ overnight to give Pt2+Theoretical loading of 0.10% of Pt respectively2+/MgAl-LDHs@Al2O3。
The evaluation of the catalytic performance with the Pt metal catalyst of comparative example 2 was performed on a microtube type catalyst evaluation device. 1g of Pt metal catalyst precursor was weighed, charged into a thermocouple well in the reaction tube, and the remaining part was filled with quartz sand. Firstly, the catalyst is reduced in situ on line, and reducing gas H is introduced2The volume space velocity is set to be H2Under atmosphere (40mL min)-1) And raising the temperature to 400 ℃ for 2h at 5 ℃ for min. The average size of Pt metal center is less than 0.8nm atom cluster. After the temperature of the reaction tube is reduced to 200 ℃, the pressure of the whole device is increased to 3MPa through a back pressure valve. An ethanol solution of furfuryl alcohol was pumped at 100. mu.l.min by a liquid feed pump-1Injecting into a reactor, opening a circulating condensing device, collecting liquid products in a gas-liquid separation tank, and sampling once every 1 h. The catalytic product is analyzed on line by gas chromatography, and the conversion rate of furfuryl alcohol is 41 percent and the selectivity of 1, 2-pentanediol is 43 percent under the stable reaction state are measured. The selectivity of tetrahydrofurfuryl alcohol is 37%.
Example 3
Step A: using in situThe growth method is to grow MgAl-LDHs in situ on gamma-Al2O3A surface. First, 11mmol Mg (NO) was added to 5.5mL deionized water3)2·6H2Dissolving O and 33mmol of urea to prepare Mg2+-a urea solution. Then, the prepared solution is poured into the solution filled with the gamma-Al2O3Pellets (5g) were placed in a 15ml autoclave and then placed in a shaker and shaken for 1 h. Finally, crystallizing in an oven at 120 ℃ for 12 hours. After crystallization is finished, the obtained solid is washed by deionized water for many times until the solid is neutral. Drying was carried out at 60 ℃ overnight. To prepare MgAl-LDHs @ Al2O3
And B: adopting an incipient wetness impregnation method to prepare MgAl-LDHs @ Al2O3Upper load of Pt2+. Firstly, the [ Pt (NH)3)4](NO3)2Dissolved in deionized water. Dropwise adding the uniformly mixed solution into the prepared MgAl-LDHs @ Al2O3A10 ml flask was then placed in a shaker and shaken for 1 h. Drying at 60 ℃ overnight to give Pt2+Theoretical loading of 0.15% of Pt respectively2+/MgAl-LDHs@Al2O3。
The Pt metal catalyst precursor of example 3 was used on a microtubular catalyst evaluation unit. 1g of Pt metal catalyst precursor was weighed, charged into a thermocouple well in the reaction tube, and the remaining part was filled with quartz sand. Firstly, the catalyst is reduced in situ on line, and reducing gas H is introduced2The volume space velocity is set to be H2Under atmosphere (40mL min)-1) And raising the temperature to 400 ℃ for 2h at 5 ℃ for min. The average size of Pt metal centers is about 0.9nm atom cluster. After the temperature of the reaction tube is reduced to 200 ℃, the pressure of the whole device is increased to 3MPa through a back pressure valve. An ethanol solution of furfuryl alcohol was pumped at 100. mu.l.min by a liquid feed pump-1Injecting into a reactor, opening a circulating condensing device, collecting liquid products in a gas-liquid separation tank, and sampling once every 1 h. The catalytic product is analyzed on line by gas chromatography, and the conversion rate of furfuryl alcohol is 65% and the selectivity of 1, 2-pentanediol is 64% under the stable reaction state are measured. The selectivity of tetrahydrofurfuryl alcohol is 15%.
Example 4
Step A: MgAl-LDHs is grown in situ on gamma-Al by using an in-situ growth method2O3A surface. First, 11mmol Mg (NO) was added to 5.5mL deionized water3)2·6H2Dissolving O and 33mmol of urea to prepare Mg2+-a urea solution. Then, the prepared solution is poured into the solution filled with the gamma-Al2O3Pellets (5g) were placed in a 15ml autoclave and then placed in a shaker and shaken for 1 h. Finally, crystallizing in an oven at 120 ℃ for 12 hours. After crystallization is finished, the obtained solid is washed by deionized water for many times until the solid is neutral. Drying was carried out at 60 ℃ overnight. To prepare MgAl-LDHs @ Al2O3
And B: adopting an incipient wetness impregnation method to prepare MgAl-LDHs @ Al2O3Upper load of Pt2+. Firstly, the [ Pt (NH)3)4](NO3)2Dissolved in deionized water. Dropwise adding the uniformly mixed solution into the prepared MgAl-LDHs @ Al2O3A10 ml flask was then placed in a shaker and shaken for 1 h. Drying at 60 ℃ overnight to give Pt2+Theoretical loading of 0.78% of Pt respectively2+/MgAl-LDHs@Al2O3。
The Pt metal catalyst precursor of example 4 was used on a microtubular catalyst evaluation unit. 1g of Pt metal catalyst precursor was weighed, charged into a thermocouple well in the reaction tube, and the remaining part was filled with quartz sand. Firstly, the catalyst is reduced in situ on line, and reducing gas H is introduced2The volume space velocity is set to be H2Under atmosphere (40mL min)-1) And raising the temperature to 400 ℃ for 2h at 5 ℃ for min. Clusters of atoms with an average size of Pt metal centres of about 1.2nm were obtained. After the temperature of the reaction tube is reduced to 200 ℃, the pressure of the whole device is increased to 3MPa through a back pressure valve. An ethanol solution of furfuryl alcohol was pumped at 100. mu.l.min by a liquid feed pump-1Injecting into a reactor, opening a circulating condensing device, collecting liquid products in a gas-liquid separation tank, and sampling once every 1 h. The catalytic product is analyzed on line by gas chromatography, and the conversion rate of furfuryl alcohol is 98% and the selectivity of 1, 2-pentanediol is 83% under the stable reaction state are measured. The selectivity of tetrahydrofurfuryl alcohol is 7%.
Claims (3)
1. The method for efficiently hydrogenating and converting the furfuryl alcohol is characterized by being carried out on a miniature fixed bed reaction device, wherein the catalyst is a Pt-containing catalyst, the reaction pressure is 0-3 MPa and is not 0, an ethanol solution of the furfuryl alcohol enters a gasification chamber of the device through a liquid pressure pump and reacts with a gas H2Uniformly mixing the mixture and entering a reactor, wherein the reaction temperature is 160-300 ℃;
the Pt-containing catalyst is composed of a Pt metal active center and a composite oxide obtained by calcining hydrotalcite, wherein the Pt metal active center is uniformly dispersed, the content of the Pt metal active center in the catalyst is 0.08-1.67 wt%, the Pt metal active center is a single atom or an atomic cluster, and the particle size of the atomic cluster is 0.9-1.6 nm;
on the monoatomic Pt, the selectivity of generating the 2-methylfuran by hydrogenating and converting the furfuryl alcohol is high; on the atomic cluster Pt, the selectivity of 1, 2-pentanediol generated by the hydroconversion of furfuryl alcohol is high.
2. A process for the high efficiency hydroconversion of furfuryl alcohol as claimed in claim 1, wherein furfuryl alcohol is reacted with H2Is 1/100.
3. A process for the high efficiency hydroconversion of furfuryl alcohol as claimed in claim 1, comprising the steps of: preparation of Pt-containing catalyst: the double metal composite hydroxide is also called hydrotalcite as carrier, and the divalent cation of hydrotalcite laminate selects Mg2+The trivalent cation is Al3+(ii) a Growing hydrotalcite in situ on gamma-Al by in-situ growth method2O3A surface; prepared hydrotalcite carrier impregnated Pt2+Solution to be impregnated with Pt2+The precursor of the post hydrotalcite sample is in H2Reducing in atmosphere, controlling the reduction temperature at 300-400 ℃, and controlling the reduction time at 60-120min to obtain the Pt-containing catalyst; to obtain a monoatomic Pt metal active center in H2Calcining in air before reduction at 400 ℃ at 300 ℃ for 60-120 min.
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