CN111939899B - Graphene oxide loaded ruthenium-based catalyst, preparation and application in lignin degradation - Google Patents
Graphene oxide loaded ruthenium-based catalyst, preparation and application in lignin degradation Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 39
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000015556 catabolic process Effects 0.000 title claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000004108 freeze drying Methods 0.000 claims abstract description 11
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000011837 pasties Nutrition 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- JKSGBCQEHZWHHL-UHFFFAOYSA-N 2-phenoxyethylbenzene Chemical compound C=1C=CC=CC=1OCCC1=CC=CC=C1 JKSGBCQEHZWHHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 5
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 239000001301 oxygen Substances 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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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Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a graphene oxide loaded ruthenium-based catalyst, preparation and application thereof in lignin degradation. Mixing and dissolving concentrated sulfuric acid, potassium persulfate and phosphorus pentoxide, and then adding graphite powder to stir; stirring, centrifugally filtering, and freeze-drying to obtain pre-oxidized graphite powder; then obtaining graphene oxide through low-temperature reaction, medium-temperature reaction and high-temperature reaction; adding graphene oxide into a ruthenium chloride solution, stirring the mixture to be pasty, then continuously stirring the mixture, and drying the mixture to obtain a graphene oxide loaded ruthenium-based catalyst precursor; the precursor is roasted and reduced by metal to obtain the graphene oxide supported ruthenium-based catalyst. The catalyst prepared by the invention has acidic active centers, can greatly improve the selectivity of the reaction, and has the characteristics of simple preparation method, lower cost, high catalytic degradation efficiency and the like.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a graphene oxide loaded ruthenium-based catalyst, and preparation and application thereof in lignin degradation.
Background
Due to the over-development and consumption of fossil energy, the reserves thereof have been reduced year by year, and the search for renewable energy has gradually become a hot spot of current world attention. The lignocellulose mainly comprises cellulose, hemicellulose and lignin, wherein the lignin is natural renewable organic compounds containing a second most amount in the world except the cellulose and accounts for 20-30 wt% of the lignocellulose. The lignin mainly contains rich benzene ring structures and rich oxygen-containing functional groups, so that the lignin has a very large application prospect in the aspects of producing chemicals and alternative energy substances, and in the past decades, as more lignin waste liquid generated by papermaking is generated, the lignin is recycled, and the lignin is used for producing value-added chemicals, so that the research on alternative fuels and platform compounds becomes particularly important. However, due to the complexity of lignin structure and the randomness of the depolymerization process, the lignin degradation products are now relatively complex, and it is still a great challenge to develop catalysts for efficient lignin degradation and to explore efficient lignin to aromatic product conversion pathways.
At present, noble metals and non-noble metals are mainly used as catalytic active centers for lignin catalyst degradation, wherein the non-noble metals mainly comprise metal elements such as Ni, cu, fe, co and the like as the active centers of the catalysts, and the Ni element has a remarkable effect on hydrogenation selectivity. In the aspect of noble metals, ru, pd and Rh are used as active centers of the catalyst, wherein the Ru has very high activity in hydrogenation reaction and is a catalyst which is very valuable for degrading lignin and extracting effective chemicals, but the Ru catalyst preferentially generates naphthenic substances due to the over-strong hydrogenation capacity, so that the Ru catalyst is not favorable for efficiently degrading lignin and can cause the difficulty in breaking C-O bonds with the highest lignin content subsequently. Graphene oxide is used as a novel two-dimensional material, is widely applied at present, and has a great number of oxygen-containing functional groups on the superior specific surface and the surface, so that the graphene oxide has a great application prospect in the field of catalysis. The surface of the catalyst is rich in oxygen-containing functional groups, so that the catalyst is rich in acidity, C-O can be preferentially and selectively broken in lignin degradation, the Ru metal catalyst can be effectively combined, and the catalyst has a very great prospect in the field of lignin explanation.
Disclosure of Invention
In order to solve the defects and shortcomings in the prior art, the invention mainly aims to provide a preparation method of a graphene oxide loaded ruthenium-based catalyst, which has the advantages of simple and convenient preparation method, low energy consumption, simple material acquisition and the like.
The other purpose of the invention is to provide the graphene oxide loaded ruthenium-based catalyst prepared by the preparation method, the catalyst has an acidic active center, can greatly improve the selectivity of the reaction, and has the characteristics of high stability and selectivity, capability of efficiently degrading lignin and the like compared with other noble metal catalysts.
The invention further aims to provide application of the graphene oxide loaded ruthenium-based catalyst.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a graphene oxide loaded ruthenium-based catalyst comprises the following steps:
(1) Mixing and dissolving concentrated sulfuric acid, potassium persulfate and phosphorus pentoxide, and then adding graphite powder and stirring; stirring, centrifugally filtering, and freeze-drying to obtain pre-oxidized graphite powder;
(2) Uniformly stirring concentrated sulfuric acid and sodium nitrate to obtain a mixed solution; under the condition of low temperature, adding the pre-oxidized graphite powder prepared in the step (1) into the mixed solution, uniformly stirring, adding potassium permanganate and carrying out low-temperature reaction; after the low-temperature reaction is finished, carrying out medium-temperature reaction; after the medium-temperature reaction is finished, adding water for high-temperature reaction; after the high-temperature reaction is finished, adding water to terminate the reaction, and then carrying out centrifugal filtration, washing and freeze drying to obtain graphene oxide;
(3) Dissolving ruthenium chloride trihydrate into water to obtain a ruthenium chloride solution; adding the graphene oxide prepared in the step (2) into a ruthenium chloride solution, stirring the mixture to be pasty, then continuously stirring the mixture, and drying the mixture to obtain a graphene oxide loaded ruthenium-based catalyst precursor;
(4) Roasting the product dried in the step (4) under the condition of introducing nitrogen; then reducing the metal under the condition of introducing hydrogen to obtain a graphene oxide loaded ruthenium-based catalyst (Ru/GO catalyst);
the volume mass ratio (ml: g) of the concentrated sulfuric acid to the graphite powder in the step (1) is preferably (15-50): (1-10);
the mass ratio of the potassium persulfate to the phosphorus pentoxide to the graphite powder in the step (1) is preferably (1.0-10): (1.0-10): (1-10);
the stirring condition in the step (1) is preferably that the stirring is carried out for 0.5 to 12 hours at a temperature of between 25 and 100 ℃;
the mass-volume-mass ratio (g: ml: g) of the pre-oxidized graphite powder, the concentrated sulfuric acid and the sodium nitrate in the step (2) is preferably (1-10): (15-85): (1-5);
the mass ratio of the pre-oxidized graphite powder to the potassium permanganate in the step (2) is preferably (1:3) - (1:6);
the low temperature in the step (2) is preferably 0-5 ℃;
the low-temperature reaction condition in the step (2) is preferably 0-5 ℃ and stirring for reaction for 1-2 h;
the condition of the medium-temperature reaction in the step (2) is preferably that the stirring reaction is carried out for 0.5 to 1 hour at the temperature of between 30 and 45 ℃;
the high-temperature reaction condition in the step (2) is preferably that the stirring reaction is carried out for 0.5 to 1 hour at the temperature of between 95 and 100 ℃;
the volume mass ratio (ml: g) of the water added after the medium-temperature reaction in the step (2) to the preliminarily oxidized graphite powder is preferably (80-300): (1-10);
the volume mass ratio (ml: g) of the water added after the high-temperature reaction in the step (2) to the preliminarily oxidized graphite powder is preferably (150-1000): (1-10);
the concentration of the ruthenium chloride solution in the step (3) is preferably 0.01-0.05 g/ml;
the condition of continuous stirring in the step (3) is preferably that the stirring is carried out for 6 to 24 hours at the temperature of between 25 and 80 ℃;
the drying condition in the step (3) is preferably 80-120 ℃ for 9-24 h;
the roasting condition in the step (4) is preferably 200-350 ℃ for 1-6 h, wherein the flow rate of nitrogen gas is 20-100 ml/min;
the condition of metal reduction in the step (4) is preferably that the metal is reduced for 1 to 6 hours at the temperature of between 150 and 350 ℃, wherein the flow rate of hydrogen gas is 20 to 100ml/min;
the graphene oxide loaded ruthenium-based catalyst is prepared by the preparation method;
in the graphene oxide loaded ruthenium-based catalyst, the mass content of Ru relative to graphene oxide is 1-5%;
the graphene oxide supported ruthenium-based catalyst is applied to degradation of lignin or lignin model compounds;
the lignin model compound is preferably phenoxyethylbenzene;
the application comprises the following steps:
mixing the graphene oxide loaded ruthenium-based catalyst, methanol and a lignin model compound, and carrying out high-pressure heating reaction; filtering and recovering the graphene oxide loaded ruthenium-based catalyst after the reaction is finished;
the volume-mass molar ratio (mg: ml: mmol) of the graphene oxide-loaded ruthenium-based catalyst, methanol and lignin model compound is preferably (5-100): (5-20): (0.5 to 10);
the reaction conditions are as follows: the rotating speed is 500 rpm-1200 rpm, the temperature is 100 ℃ to 220 ℃, the hydrogen pressure is 0.5 MPa-4 MPa, and the reaction time is 1 h-12 h;
compared with the prior art, the invention has the following advantages and beneficial effects:
(1) Compared with other metal catalyst preparation methods, the preparation method of the graphene oxide loaded ruthenium-based catalyst provided by the invention has the characteristics of simple material acquisition, simple and convenient manufacturing method, low cost, large specific surface area of the product, capability of efficiently degrading lignin, high degradation yield of 99% in a lignin model compound and the like.
(2) The graphene oxide supported ruthenium-based catalyst (figure 1) provided by the invention combines the advantages of ruthenium metal and graphene oxide in catalytic performance, improves the performance of the catalyst to the maximum, improves the overall activity of the catalyst by adding a small amount of ruthenium metal, maintains the high selectivity of the catalyst, and can play a great role in degrading lignin.
Drawings
FIG. 1 is a schematic of the structure of a Ru/GO catalyst made by the present invention.
FIG. 2 is an SEM image of the 5% Ru/GO catalyst prepared in example 1.
FIG. 3 Infrared spectrum of 5% Ru/GO catalyst prepared in example 1.
FIG. 4 is an X-ray energy spectrum of 5% Ru/GO catalyst prepared in example 1.
FIG. 5 is a graph of the results of 5% Ru/GO catalyst degradation of lignin model compounds, as prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The concentrated sulfuric acid in the examples is commercially available.
Example 1
(1) Adding 30ml of concentrated sulfuric acid, 2.5g of potassium persulfate and 2.5g of phosphorus pentoxide into a beaker, ultrasonically stirring until the mixture is uniform, slowly adding 5g of graphite powder, and continuously stirring for 8 hours at 60 ℃; after stirring, centrifugally filtering, and then freeze-drying to obtain pre-oxidized graphite powder;
(2) Mixing 85ml of concentrated sulfuric acid and 2.5g of sodium nitrate, and uniformly stirring to obtain a mixed solution; slowly adding 5g of the pre-oxidized graphite powder prepared in the step (1) into the mixed solution, uniformly stirring at 4 ℃, then slowly adding 15g of potassium permanganate, and continuously stirring for 1h at 4 ℃ to fully react; after the low-temperature reaction is finished, the stirring temperature is increased to 45 ℃ and stirred for 0.5h; after the medium temperature reaction is finished, 200ml of deionized water is added, and the mixture is continuously stirred for 0.5h at 100 ℃; after the high-temperature reaction is finished, 500ml of deionized water is added to stop the reaction; centrifuging at a high speed, filtering, washing to be neutral, and freeze-drying to obtain graphene oxide powder;
(3) Weighing 0.26g of ruthenium chloride trihydrate and 5g of deionized water, and ultrasonically stirring to dissolve the ruthenium chloride to obtain a ruthenium chloride solution; adding 2g of graphene oxide powder prepared in the step (2) into a ruthenium chloride solution, stirring to fully mix the graphene oxide powder and the solution to be pasty, then dipping and stirring at the normal temperature of 25 ℃ for 6h, and after the dipping and stirring, putting into a vacuum drying oven to dry at the temperature of 80 ℃ for 24h;
(4) Putting the dried product in the step (3) into a tubular furnace, and roasting for 3h at 250 ℃ under the condition of introducing nitrogen (flow rate of 50 ml/min); after the reaction is finished, introducing hydrogen, and reducing at a high temperature of 250 ℃ for 3h, wherein the hydrogen flow rate is 50ml/min, and obtaining the graphene oxide loaded ruthenium-based catalyst (5% of Ru/GO catalyst, wherein 5% refers to the mass content of Ru relative to graphene oxide) after the reaction is finished; wherein, FIG. 2 is an SEM image of the catalyst. FIG. 3 is an infrared spectrum of the catalyst, from which it can be seen that 3 420cm -1 A wide and strong-OH stretching vibration characteristic peak exists; 1726cm -1 Corresponds to a characteristic peak of the stretching vibration with C = O; at 1 625cm -1 Corresponding to the characteristic peak of the stretching vibration with C = C; at 1390 and 1050cm -1 The asymmetric stretching vibration peak corresponding to C = O and the stretching vibration absorption peak corresponding to C-O respectively, and the existence of the oxygen-containing functional groups on the GO surface proves that the graphite is oxidized. Fig. 4 is an X-ray energy spectrum of the catalyst, from which it can be seen that a characteristic peak of ruthenium element appears and its normalized relative content is 4.95%.
(5) 20mg of the 5% Ru/GO catalyst prepared in step (4), 1mmol of phenoxyethylbenzene and 10ml of methanol were added to an autoclave, and the mixture was stirred by ultrasound to mix them uniformly, then the reaction was started under the conditions of introducing 2MPa of hydrogen, rotating at 1000rpm, and heating to 130 ℃, and finally the product (FIG. 5) was collected and analyzed by GC-MS. Yield calculation formula: (molar amount of reaction produced/total molar amount of reaction) × 100%, conversion calculation formula: (molar amount of consumed reactant/total molar amount of charged reactant) × 100%.
Example 2
(1) Adding 30ml of concentrated sulfuric acid, 2.5g of potassium persulfate and 2.5g of phosphorus pentoxide into a beaker, ultrasonically stirring until the mixture is uniform, slowly adding 5g of graphite powder, continuously stirring at 100 ℃ for reacting for 2 hours, centrifugally filtering after stirring, and freeze-drying to obtain pre-oxidized graphite powder;
(2) Mixing 85ml of concentrated sulfuric acid and 2.5g of sodium nitrate, and uniformly stirring to obtain a mixed solution; slowly adding 5g of the pre-oxidized graphite powder prepared in the step (1) into the mixed solution, uniformly stirring at 2 ℃, then slowly adding 15g of potassium permanganate, and continuously stirring for 2 hours at 2 ℃ to fully react; after the low-temperature reaction is finished, the stirring temperature is increased to 40 ℃ and stirred for 1 hour; after the medium temperature reaction is finished, 200ml of deionized water is added, and the mixture is continuously stirred for 1 hour at 98 ℃; after the high-temperature reaction is finished, 500ml of deionized water is added to stop the reaction; centrifuging at a high speed, filtering, washing to be neutral, and freeze-drying to obtain graphene oxide powder;
(3) Weighing 0.15g of ruthenium chloride trihydrate and 5g of deionized water, and ultrasonically stirring to dissolve the ruthenium chloride to obtain a ruthenium chloride solution; adding 2g of graphene oxide powder prepared in the step (2) into a ruthenium chloride solution, stirring to fully mix the graphene oxide powder and the solution to be pasty, then dipping and stirring at the normal temperature of 25 ℃ for 6h, and after stirring, putting into a vacuum drying oven to dry at the temperature of 120 ℃ for 9h;
(4) Putting the dried product in the step (3) into a tubular furnace, and roasting for 3h at 250 ℃ under the condition of introducing nitrogen (flow rate of 50 ml/min); after the reaction is finished, introducing hydrogen, and reducing at a high temperature of 250 ℃ for 3h, wherein the hydrogen flow rate is 50ml/min, and obtaining the graphene oxide loaded ruthenium-based catalyst (3% Ru/GO catalyst) after the reaction is finished;
(5) Adding 20mg of the 3-percent Ru/GO catalyst prepared in the step (4), 1mmol of phenoxyethylbenzene and 10ml of methanol into a high-pressure reaction kettle, carrying out ultrasonic stirring to uniformly mix the components, then starting reaction under the conditions of introducing 2Mpa hydrogen, rotating speed of 1000rpm and heating to 130 ℃, finally collecting a product, and feeding the obtained product into GC-MS for analysis. Yield calculation formula: (molar amount of reaction produced/total molar amount of reaction) × 100%, conversion calculation formula: (molar amount of consumed reactant/total molar amount of charged reactant) × 100%.
Example 3
(1) Adding 30ml of concentrated sulfuric acid, 2.5g of potassium persulfate and 2.5g of phosphorus pentoxide into a beaker, ultrasonically stirring until the mixture is uniform, slowly adding 5g of graphite powder, continuously stirring at 80 ℃ for reacting for 6 hours, centrifugally filtering after stirring, and freeze-drying to obtain pre-oxidized graphite powder;
(2) Mixing 85ml of concentrated sulfuric acid and 2.5g of sodium nitrate, and uniformly stirring to obtain a mixed solution; slowly adding 5g of the pre-oxidized graphite powder prepared in the step (1) into the mixed solution, uniformly stirring at 0 ℃, then slowly adding 15g of potassium permanganate, and continuously stirring for 2 hours at 0 ℃ to fully react; after the low-temperature reaction is finished, the stirring temperature is increased to 35 ℃ and stirred for 1 hour; after the medium temperature reaction is finished, 200ml of deionized water is added, and the mixture is continuously stirred for 1 hour at 98 ℃; after the high-temperature reaction is finished, 500ml of deionized water is added to stop the reaction; centrifuging at a high speed, filtering, washing to be neutral, and freeze-drying to obtain graphene oxide powder;
(3) Weighing 0.05g of ruthenium chloride trihydrate and 5g of deionized water, and ultrasonically stirring to dissolve the ruthenium chloride to obtain a ruthenium chloride solution; adding 2g of graphene oxide powder prepared in the step (2) into a ruthenium chloride solution, stirring to fully mix the graphene oxide powder and the solution to be pasty, then dipping and stirring at the normal temperature of 25 ℃ for 6h, and drying in a vacuum drying oven at the temperature of 110 ℃ for 24h after the dipping and stirring are completed;
(4) Putting the dried product in the step (3) into a tubular furnace, and roasting for 3h at 250 ℃ under the condition of introducing nitrogen (flow rate of 50 ml/min); after the reaction is finished, introducing hydrogen, and reducing at a high temperature of 250 ℃ for 3h, wherein the hydrogen flow rate is 50ml/min, and obtaining the graphene oxide loaded ruthenium-based catalyst (1% Ru/GO catalyst) after the reaction is finished;
(5) Adding 20mg of the 1-percent Ru/GO catalyst prepared in the step (4), 1mmol of phenoxyethylbenzene and 10ml of methanol into a high-pressure reaction kettle, carrying out ultrasonic stirring to uniformly mix the components, then starting reaction under the conditions of introducing 2Mpa hydrogen, rotating speed of 1000rpm and heating to 130 ℃, finally collecting a product, and feeding the obtained product into GC-MS for analysis. Yield calculation formula: (molar amount of reaction produced/total molar amount of reaction) × 100%, conversion calculation formula: (molar amount of consumed reactant/total molar amount of charged reactant) × 100%.
Table 1 shows the degradation yields of the Ru/GO catalysts obtained in examples 1, 2 and 3, with the best Ru/GO degradation conversion, as seen by 5% in Table 1; table 2 shows the 5% Ru/GO catalyst stability test obtained in example 1, which resulted in a yield of 94.6% of total conversion of the lignin-degrading model compound after 5 repeated recoveries.
Table 1 shows the degradation effects of examples 1, 2 and 3
TABLE 2 catalyst stability testing for catalyst recycle of example 1
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. An application of a graphene oxide loaded ruthenium-based catalyst in phenoxyethylbenzene degradation is characterized in that:
mixing the graphene oxide loaded ruthenium-based catalyst, methanol and phenoxyethylbenzene, and introducing hydrogen of 0.5Mpa to 4Mpa for high-pressure heating reaction; filtering and recovering the graphene oxide loaded ruthenium-based catalyst after the reaction is finished;
the preparation method of the graphene oxide loaded ruthenium-based catalyst comprises the following steps:
(1) Mixing and dissolving concentrated sulfuric acid, potassium persulfate and phosphorus pentoxide, and then adding graphite powder for stirring; stirring, centrifugally filtering, and freeze-drying to obtain pre-oxidized graphite powder;
(2) Uniformly stirring concentrated sulfuric acid and sodium nitrate to obtain a mixed solution; under the condition of low temperature, adding the pre-oxidized graphite powder prepared in the step (1) into the mixed solution, uniformly stirring, adding potassium permanganate and carrying out low-temperature reaction; after the low-temperature reaction is finished, carrying out medium-temperature reaction; after the medium-temperature reaction is finished, adding water for high-temperature reaction; after the high-temperature reaction is finished, adding water to terminate the reaction, and then carrying out centrifugal filtration, washing and freeze drying to obtain graphene oxide;
(3) Dissolving ruthenium chloride trihydrate into water to obtain a ruthenium chloride solution; adding the graphene oxide prepared in the step (2) into a ruthenium chloride solution, stirring the mixture to be pasty, then continuously stirring the mixture, and drying the mixture to obtain a graphene oxide loaded ruthenium-based catalyst precursor;
(4) Roasting the product dried in the step (3) under the condition of introducing nitrogen; then reducing the metal under the condition of introducing hydrogen to obtain a graphene oxide loaded ruthenium-based catalyst;
in the graphene oxide loaded ruthenium-based catalyst, the mass content of Ru relative to graphene oxide is 5%;
the low temperature in the step (2) is 0~5 ℃, the medium temperature is 30 to 45 ℃, and the high temperature is 95 to 100 ℃.
2. Use according to claim 1, characterized in that:
the volume mass ratio of the concentrated sulfuric acid to the graphite powder in the step (1) is (15 to 50ml): (1 to 10g);
the mass ratio of the potassium persulfate to the phosphorus pentoxide to the graphite powder in the step (1) is (1.0-10): (1.0 to 10): (1 to 10).
3. Use according to claim 1, characterized in that:
the concentration of the ruthenium chloride solution in the step (3) is 0.01 to 0.05g/ml.
4. Use according to claim 1, characterized in that:
and (3) stirring for 6 to 24h under the condition of continuously stirring at 25 to 80 ℃.
5. Use according to claim 1, characterized in that:
and (5) roasting for 1 to 6h under the roasting condition of 200 to 350 ℃, wherein the flow rate of nitrogen gas is 20 to 100ml/min.
6. Use according to claim 1, characterized in that:
and (4) carrying out metal reduction for 1 to 6h at the temperature of 150 to 350 ℃, wherein the flow rate of hydrogen gas is 20 to 100ml/min.
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