CN114029070A - In-situ hydrogenolysis aryl ether bond catalyst and preparation method and application thereof - Google Patents
In-situ hydrogenolysis aryl ether bond catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920005610 lignin Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 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 21
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 15
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 229910052593 corundum Inorganic materials 0.000 claims description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 claims description 5
- JKSGBCQEHZWHHL-UHFFFAOYSA-N 2-phenoxyethylbenzene Chemical compound C=1C=CC=CC=1OCCC1=CC=CC=C1 JKSGBCQEHZWHHL-UHFFFAOYSA-N 0.000 claims description 4
- -1 aromatic ether compound Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 2
- 150000008378 aryl ethers Chemical class 0.000 claims 5
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 7
- 239000002028 Biomass Substances 0.000 abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 229910009112 xH2O Inorganic materials 0.000 description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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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
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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
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- 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
- C07C29/19—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 in six-membered aromatic rings
- C07C29/20—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 in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2601/14—The ring being saturated
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Abstract
The invention discloses an in-situ hydrogenolysis aryl ether bond catalyst and a preparation method and application thereof, belonging to the field of biomass catalytic hydrogenolysis. The catalyst of the invention takes NiRuAl hydrotalcite as a precursor, and the NiRuAl hydrotalcite is calcined and reduced to prepare the supported high-dispersion NiRu alloy catalyst, wherein Ni and Ru respectively account for 20-40% and 1-5% of the total mass of the catalyst. The high-dispersion NiRu alloy catalyst shows excellent catalytic performance in-situ hydrogenolysis reaction of lignin and a model compound thereof, can break aromatic ether bonds in the lignin and the model compound thereof with high selectivity and high activity under mild conditions, and is obviously superior to a commercial Ru/C catalyst. The catalyst provided by the invention is simple in preparation method and good in stability, does not need additional hydrogen for catalyzing hydrogenolysis reaction of lignin and model compounds thereof, and is mild in reaction conditions, so that the catalyst has a good application prospect in the lignin conversion process.
Description
Technical Field
The invention belongs to the field of catalytic hydrogenolysis of biomass, and particularly relates to high-dispersion high-activity NiRu/Al2O3A catalyst, a preparation method thereof and application thereof in-situ catalytic hydrogenolysis of aryl ether bond.
Background
Lignin is second only to cellulose in biomass and is the only renewable aromatic source. During the process of making paper by using biomass or preparing ethanol by fermentation, a large amount of lignin waste liquor can be generated. Therefore, efficient depolymerization of lignin is important for high-value utilization of biomass. At present, methods for depolymerizing lignin mainly include pyrolysis, hydrogenolysis, liquefaction, oxidation, hydrolysis, and the like. Compared with other depolymerization methods, hydrogenolysis has the advantages of mild reaction conditions, high product yield, adjustable composition structure and the like, and is widely concerned.
The low-carbon alcohol has the advantages of strong hydrogen supply capacity, low supercritical point, easy recovery and the like, and is widely used for preparing platform compounds such as aromatic hydrocarbon, phenol, cyclohexanol and the like by hydrogenolysis of lignin. Research shows that Ru/C and Ni-based and bimetallic catalysts can promote lignin hydrogenolysis. However, the traditional bimetallic supported catalyst is prepared by an impregnation method, and has low dispersity and low activity. In recent years, hydrotalcite has attracted much attention as a catalyst precursor for preparing a highly dispersed supported catalyst due to its structure-tunable property. Therefore, the hydrotalcite-based NiRu bimetallic catalyst has important significance for catalyzing the in-situ hydrogenolysis of lignin to prepare the platform compound for the efficient utilization of the lignin.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-dispersion high-activity NiRu/Al2O3The catalyst and the application thereof in-situ catalytic hydrogenolysis of aryl ether bonds are expected to realize the high-efficiency hydrogenolysis of lignin and model compounds thereof.
The invention is realized by the following technical scheme.
The catalyst of the invention takes NiRu alloy as a catalytic active site, and Al2O3Is a carrier; based on the total mass of the catalyst, the Ni and the Ru respectively account for 20-40 percent and 1-5 percent.
The invention provides a preparation method of the catalyst, which specifically comprises the following steps:
(1) mixing Ni (NO) with the molar ratio of 1-3:0.5-2:0.02-0.13)2 .6H2O、Al(NO3)3 .9H2O and RuCl3 .xH2Adding O into water, stirring, and adding Na dropwise with NaOH solution of certain concentration (0.5-3mol/L)2CO3Heating the solution to 60-80 ℃ and aging for 5-20 h; and then centrifuging, washing and drying to obtain the NiRuAl hydrotalcite.
(2) And (2) calcining the NiRuAl hydrotalcite obtained in the step (1) at the high temperature of 300-600 ℃ for 2-6 hours to obtain the NiRuAl composite oxide.
(3) By H2Reduction step (2) to obtainTo the resulting NiRuAl composite oxide, cooling and then adding O2Passivating for 1-3h to obtain a target product: NiRu/Al2O3A catalyst.
Further, the pH value of the solution in the step (1) is maintained at 9-11.
Further, H in the step (3)2The reduction heating rate is 2 ℃/min, the reduction temperature is 450-.
The invention also provides the application of the catalyst prepared by the method in-situ aryl ether bond hydrogenolysis, which comprises the following steps:
mixing NiRu/Al2O3Adding the catalyst, the hydrogen source and the aromatic ether compound into a reaction kettle according to the dosage ratio of 20-50mg:5-20mL:1mmol, sealing, filling 10bar of protective gas, and reacting at 100-240 ℃ for l-8h to obtain the hydrogenolysis product.
Further, the hydrogen source is one of methanol, ethanol and isopropanol.
Furthermore, the aryl ether compound is one of phenyl benzyl ether, phenyl phenethyl ether, diphenyl ether and lignin.
Compared with the prior art, the invention has the following technical effects:
1. the catalyst has high dispersity (average particle size of about 6nm, shown in figures 1 and 2) and high activity, takes alcohol as a hydrogen source, and does not need additional H2The hydrogenolysis cleavage of the aryl ether bond can be realized at a lower reaction temperature (100 ℃).
2. The preparation method of the catalyst is simple, and the hydrotalcite precursor is prepared by adopting a coprecipitation method, so that the high-dispersion load type NiRu alloy catalyst is prepared.
3. The high-dispersion NiRu alloy catalyst shows excellent catalytic performance in-situ hydrogenolysis reaction of lignin and a model compound thereof, can break aromatic ether bonds in the lignin and the model compound thereof with high selectivity and high activity under mild conditions, and is obviously superior to a commercial Ru/C catalyst.
4. The catalyst of the invention has good stability, still keeps high activity after being recycled for 5 times, and can be separated by a magnetic field.
5. The lignin belongs to a byproduct of papermaking and biorefinery, and the high-efficiency conversion of the lignin has great significance for the high-valued utilization of biomass. The catalyst of the invention has simple preparation method, good stability and mild reaction conditions, thereby having good application prospect in the lignin conversion process.
Drawings
FIG. 1 shows NiRu/Al in example 1 of the present invention2O3XRD pattern of the catalyst;
as can be seen, NiRu/Al2O3The active components Ni and Ru in the catalyst are highly dispersed.
FIG. 2 shows NiRu/Al in example 1 of the present invention2O3HRTEM at different magnifications of the catalyst;
NiRu/Al calculated by measurement of FIG. 2b2O3The average particle size of the active component NiRu in the catalyst is 5.8nm, which also indicates that the dispersion degree of the active component is higher, and the lattice fringe of Ni (111) is consistent with the XRD analysis result as can be seen from figure 2 c.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1:
mixing Ni (NO) with a molar ratio of 2:1:0.053)2 .6H2O、Al(NO3)3 .9H2O, and RuCl3 .xH2O is added into water and fully stirred, and is added into Na dropwise simultaneously with 1mol/L NaOH solution2CO3In the solution, the pH value of the solution is maintained at 10, and the solution is heated to 60 ℃ and aged for 20 h. And centrifuging, washing and drying after the aging is finished to obtain the NiRuAl hydrotalcite structure. And calcining the NiRuAl hydrotalcite at 460 ℃ for 6 hours to obtain the NiRuAl composite oxide. By H2Reducing the NiRuAl composite oxide at 500 ℃, cooling and then using O2Passivating for 1h to obtain NiRu/Al2O3A catalyst. Characterization by XRD (FIG. 1) and HRTEM (FIG. 2) showed that the NiRu/Al prepared2O3The active components Ni and Ru in the catalyst are highly dispersed, and the average grain diameter is about 6 nm. Mixing NiRu/Al2O3Adding the catalyst, isopropanol and phenyl benzyl ether into a reaction kettle according to the dosage ratio of 25mg:20mL:0.5mmol, sealing, introducing 10bar of protective gas, and reacting at 100 ℃ for 4h to obtain a hydrogenolysis product. The phenyl benzyl ether conversion was 97.6% and the products were predominantly toluene, phenol and cyclohexanol, with yields of 44.8%, 16.2% and 36.7%, respectively. After the catalyst is recycled for 5 times, the conversion rate of the phenyl benzyl ether is still as high as 95.1 percent.
Example 2:
mixing Ni (NO) with a molar ratio of 2:1:0.053)2 .6H2O、Al(NO3)3 .9H2O, and RuCl3 .xH2O is added into water and fully stirred, and is added into Na dropwise simultaneously with 2mol/L NaOH solution2CO3In the solution, the pH value of the solution is maintained at 10, and the solution is heated to 60 ℃ and aged for 20 h. And centrifuging, washing and drying after the aging is finished to obtain the NiRuAl hydrotalcite structure. And calcining the NiRuAl hydrotalcite at 460 ℃ for 6 hours to obtain the NiRuAl composite oxide. By H2Reducing the NiRuAl composite oxide at 550 ℃, cooling and then using O2Passivating for 1h to obtain NiRu/Al2O3A catalyst. Mixing NiRu/Al2O3Adding the catalyst, isopropanol and diphenyl ether into a reaction kettle according to the dosage ratio of 25mg:20mL:0.5mmol, sealing, filling 10bar of protective gas, and reacting at 140 ℃ for 3h to obtain a hydrogenolysis product. The conversion of diphenyl ether was 100%, the products were mainly benzene, cyclohexane and cyclohexanol, the yields were 8.0%, 39.4% and 52.6%, respectively.
Example 3:
mixing Ni (NO) with a molar ratio of 2:1:0.053)2 .6H2O、Al(NO3)3 .9H2O, and RuCl3 .xH2O is added into water and fully stirred, and is added into Na dropwise simultaneously with 2.5mol/L NaOH solution2CO3In the solution, the pH value of the solution is maintained at 10, and the solution is heated to 60 ℃ and aged for 20 h. After aging, separatingAnd (4) carrying out core washing and drying to obtain the NiRuAl hydrotalcite structure. And calcining the NiRuAl hydrotalcite at 460 ℃ for 6 hours to obtain the NiRuAl composite oxide. By H2Reducing the NiRuAl composite oxide at 500 ℃, cooling and then using O2Passivating for 1h to obtain NiRu/Al2O3A catalyst. Mixing NiRu/Al2O3Adding the catalyst, isopropanol and phenyl phenethyl ether into a reaction kettle according to the dosage ratio of 25mg to 20mL to 0.5mmol, sealing, filling 10bar of protective gas, and reacting at 120 ℃ for 4h to obtain a hydrogenolysis product. The conversion of phenyl phenethyl ether was 96.5% and the products were mainly ethylbenzene, phenol and cyclohexanol, with yields of 44.4%, 18.8% and 20.9%, respectively. Is obviously superior to the commercial Ru/C catalyst, and the conversion rate under the same conditions is only 9.5 percent.
Example 4:
mixing Ni (NO) with a molar ratio of 3:1:0.053)2 .6H2O、Al(NO3)3 .9H2O, and RuCl3 .xH2O is added into water and fully stirred, and is added into Na dropwise simultaneously with 0.5mol/L NaOH solution2CO3In the solution, the pH value of the solution is maintained at 11, and the solution is heated to 60 ℃ and aged for 20 h. And centrifuging, washing and drying after the aging is finished to obtain the NiRuAl hydrotalcite structure. And calcining the NiRuAl hydrotalcite at 460 ℃ for 6 hours to obtain the NiRuAl composite oxide. By H2Reducing the NiRuAl composite oxide at 500 ℃, cooling and then using O2Passivating for 1h to obtain NiRu/Al2O3A catalyst. Mixing NiRu/Al2O3Adding the catalyst, isopropanol and lignin into a reaction kettle according to the dosage ratio of 250mg to 20mL to 500mg, sealing, filling 10bar of protective gas, and reacting at 200 ℃ for 4h to obtain a hydrogenolysis product. The lignin conversion was 62.6% and the methanol solubles yield was 57.2%, with 63.6% monomer and dimer.
Example 5:
mixing Ni (NO) with a molar ratio of 3:1:0.053)2 .6H2O、Al(NO3)3 .9H2O, and RuCl3 .xH2O is added into water and fully stirred, and is added into Na dropwise simultaneously with 3mol/L NaOH solution2CO3In the solution, the pH value of the solution is maintained at 11, and the solution is heated to 60 ℃ and aged for 20 h. And centrifuging, washing and drying after the aging is finished to obtain the NiRuAl hydrotalcite structure. And calcining the NiRuAl hydrotalcite at the high temperature of 500 ℃ for 4 hours to obtain the NiRuAl composite oxide. By H2Reducing the NiRuAl composite oxide at 500 ℃, cooling and then using O2Passivating for 1h to obtain NiRu/Al2O3A catalyst. Mixing NiRu/Al2O3Adding the catalyst, isopropanol and lignin into a reaction kettle according to the dosage ratio of 250mg to 20mL to 500mg, sealing, filling 10bar of protective gas, and reacting at 220 ℃ for 4h to obtain a hydrogenolysis product. The lignin conversion was 65.9% and the methanol solubles yield was 58.1%, with monomers and dimers accounting for 72.8%.
Example 6:
mixing Ni (NO) with a molar ratio of 3:1:0.043)2 .6H2O、Al(NO3)3 .9H2O, and RuCl3 .xH2O is added into water and fully stirred, and is added into Na dropwise simultaneously with 2mol/L NaOH solution2CO3In the solution, the pH value of the solution is maintained at 10, and the solution is heated to 60 ℃ and aged for 20 h. And centrifuging, washing and drying after the aging is finished to obtain the NiRuAl hydrotalcite structure. And calcining the NiRuAl hydrotalcite at 460 ℃ for 6 hours to obtain the NiRuAl composite oxide. By H2Reducing the NiRuAl composite oxide at 550 ℃, cooling and then using O2Passivating for 1h to obtain NiRu/Al2O3A catalyst. Mixing NiRu/Al2O3Adding the catalyst, isopropanol and lignin into a reaction kettle according to the dosage ratio of 250mg to 20mL to 500mg, sealing, filling 10bar of protective gas, and reacting at 180 ℃ for 4h to obtain a hydrogenolysis product. The lignin conversion was 59.0% and the methanol solubles yield was 55.9%, with 60.5% monomer and dimer.
Claims (8)
1. The in-situ hydrogenolysis aryl ether bond catalyst is characterized in that the catalyst uses NiRu alloy as catalytically active site, Al2O3Is a carrier; based on the total mass of the catalyst, the proportion of Ni and Ru is 20-40% and 1-5% respectively.
2. The method of claim 1, comprising the steps of:
(1) mixing Ni (NO) with the molar ratio of 1-3:0.5-2:0.02-0.13)2 .6H2O、Al(NO3)3 .9H2O and RuCl3 .xH2Adding O into water, stirring, and adding Na dropwise with 0.5-3mol/L NaOH solution2CO3Heating the solution to 60-80 ℃ and aging for 5-20 h; then centrifuging, washing and drying to obtain NiRuAl hydrotalcite;
(2) calcining the NiRuAl hydrotalcite obtained in the step (1) at the high temperature of 300-600 ℃ for 2-6 hours to obtain a NiRuAl composite oxide;
(3) by H2Reducing the NiRuAl composite oxide obtained in the step (2), cooling and then using O2Passivating for 1-3h to obtain a target product: NiRu/Al2O3A catalyst.
3. The method for preparing a catalyst for in situ hydrogenolysis of aryl ether linkage as claimed in claim 2 wherein the solution pH in step (1) is maintained between 9 and 11.
4. The method for preparing a catalyst for in situ hydrogenolysis of aryl ether linkage as claimed in claim 2 wherein in step (3) H is2The reduction heating rate is 2 ℃/min, the reduction temperature is 450-.
5. Use of the catalyst of claim 1 for in situ hydrogenolysis of aryl ether linkages.
6. The use of a catalyst according to claim 5 for in situ hydrogenolysis of aryl ether linkages comprising the steps of:
mixing NiRu/Al2O3Adding the catalyst, the hydrogen source and the aromatic ether compound into a reaction kettle according to the dosage ratio of 20-50mg:5-20mL:1mmol, sealing, filling 10bar of protective gas, and reacting at 100-240 ℃ for l-8h to obtain the hydrogenolysis product.
7. The use of the catalyst of claim 6 for in situ hydrogenolysis of an aryl ether bond wherein the hydrogen source is one of methanol, ethanol and isopropanol.
8. The use of the catalyst of claim 6 for in situ hydrogenolysis of an aryl ether linkage wherein the aryl ether compound is one of phenyl benzyl ether, phenyl phenethyl ether, diphenyl ether and lignin.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115041190A (en) * | 2022-05-13 | 2022-09-13 | 安徽工业大学 | Hydrotalcite topology transition high-dispersion Ni-Ru/Al 2 O 3 Preparation of catalyst and its use |
| CN115364862A (en) * | 2022-09-20 | 2022-11-22 | 南京师范大学 | Nickel-based catalyst, preparation method and application in lignin depolymerization process |
| CN115646495A (en) * | 2022-10-18 | 2023-01-31 | 中国矿业大学 | High-activity NiCu/Al 2 O 3 Preparation of catalyst and application thereof in aspect of catalyzing hydrogen transfer cracking by C-O bond of aryl ether |
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2021
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115041190A (en) * | 2022-05-13 | 2022-09-13 | 安徽工业大学 | Hydrotalcite topology transition high-dispersion Ni-Ru/Al 2 O 3 Preparation of catalyst and its use |
| CN115364862A (en) * | 2022-09-20 | 2022-11-22 | 南京师范大学 | Nickel-based catalyst, preparation method and application in lignin depolymerization process |
| CN115646495A (en) * | 2022-10-18 | 2023-01-31 | 中国矿业大学 | High-activity NiCu/Al 2 O 3 Preparation of catalyst and application thereof in aspect of catalyzing hydrogen transfer cracking by C-O bond of aryl ether |
| CN115646495B (en) * | 2022-10-18 | 2024-03-26 | 中国矿业大学 | High-activity NiCu/Al 2 O 3 Preparation of catalyst and application of catalyst in catalytic hydrogen transfer cracking of aryl ether C-O bond |
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