CN113717746B - Hydrodeoxygenation method for biological oil - Google Patents
Hydrodeoxygenation method for biological oil Download PDFInfo
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- CN113717746B CN113717746B CN202111156761.2A CN202111156761A CN113717746B CN 113717746 B CN113717746 B CN 113717746B CN 202111156761 A CN202111156761 A CN 202111156761A CN 113717746 B CN113717746 B CN 113717746B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention discloses a hydrodeoxygenation method for biological oil, which comprises the steps of placing the biological oil into an H-type electrolytic tank to load Pt/CeO 2 Constant potential electrochemical hydrodeoxygenation with/C catalyst, mild reaction condition, high selectivity, clean and pollution-free process flowThe process is simple, the reaction is easy to control, and the hydrogenation efficiency is high.
Description
Technical Field
The invention belongs to the field of hydrogen oil preparation, and particularly relates to a biological oil hydrodeoxygenation method.
Background
With the increasing consumption of non-renewable resources such as petroleum, the search for new energy substitutes is urgent. Biomass is an ideal organic carbon source for replacing petroleum production fuels and chemicals at present. In the conversion of traditional energy into biomass energy, how to convert inexpensive biomass into fuels and chemicals at low cost is important. By pyrolysis of many biomass (wood, agricultural waste, etc.) under certain conditions, 50% -90% of the energy in the biomass can be transferred to the bio-oil. The biological oil has higher oxygen content, lower heat value compared with common fuel oil, is acidic and has chemical instability, and the biological oil must be subjected to quality improvement before practical application. Therefore, the design of the bio-oil quality improvement method which has the advantages of mild reaction conditions, high selectivity, cleanness, no pollution, simple process flow and easy control of reaction has important significance for the new energy field.
Disclosure of Invention
The invention aims to provide a biological oil quality improving method which has mild reaction conditions, high selectivity, cleanness, no pollution, simple process flow and easy control of reaction, and provides a biological oil hydrodeoxygenation method.
The invention adopts the following technical scheme:
the hydrodeoxygenation method for the biological oil is characterized by comprising the following steps of: placing biological oil into H-type electrolytic tank to load Pt/CeO 2 Carrying out potentiostatic electrochemical hydrodeoxygenation on the catalyst;
the anode chamber and the cathode chamber of the H-shaped electrolytic tank are isolated by adopting a Nafion117 membrane, the anode of the H-shaped electrolytic tank adopts a platinum net, the cathode adopts carbon paper as a carrier, and Pt/CeO is loaded 2 a/C catalyst, which uses Ag/AgCl electrode as reference electrode;
the electrolyte in the cathode chamber of the H-type electrolytic tank comprises 47.5wt% of isopropanol, 47.5wt% of deionized water and 5wt% of acetic acid;
the electrolyte in the anode chamber of the H-type electrolytic tank is 1mol/LKOH solution taking 10 weight percent of methanol and 90 weight percent of deionized water as solvents.
Preferably, the biological oil comprises phenol, methylphenol, dimethylphenol, and furfural unsaturated oxygen-containing compounds.
Preferably, the Pt/CeO 2 The preparation steps of the catalyst comprise:
s1, a proper amount of H 2 PtCl 6 ·6H 2 O solution, glycol, ce (NO) 3 ) 3 ·6H 2 O, vulcanXC-72 adding into the flask, stirring thoroughly for 30min, and adjusting pH to 13 with 1mol/LKOH solution;
s2, the mixed solution is heated to 130 ℃ and N 2 Refluxing in oil bath for 3h under atmosphere, and cooling to room temperature;
s3, carrying out suction filtration on the solution obtained in the step S2, and transferring the suction filtration into a vacuum oven at 80 ℃ for full drying, thus obtaining the product.
Preferably, the electrolysis is performed at a negative potential.
Preferably, the Pt/CeO 2 3.9. 3.9mMH for the catalyst/C 2 PtCl 6 ·6H 2 O solution, 100mL of ethylene glycol, 51-202mgCe (NO) 3 ) 3 ·6H 2 O and 80-140mgVulcanXC-72 are used as raw materials.
Preferably, the Pt/CeO 2 The catalyst/C adopts 151mgCe (NO) 3 ) 3 ·6H 2 O is used as a raw material.
The beneficial effects are that: the invention relates to a method for hydrodeoxygenation of biological oil, which comprises the steps of placing the biological oil into an H-type electrolytic tank to load Pt/CeO 2 The catalyst/C is subjected to constant potential electrochemical hydrodeoxygenation, and has the advantages of mild reaction conditions, high selectivity, cleanness, no pollution, simple process flow, easy control of reaction and high hydrogenation efficiency.
Drawings
FIG. 1 shows the conversion rate of bio-oil after electrocatalytic benzaldehyde with different cerium oxide content catalysts in example 1 is subjected to constant potential electrolytic hydrogenation for 4 hours at different potentials;
FIG. 2 shows the bio-oil conversion rate of the benzaldehyde, furfural, phenol and lactic acid in example 2 after constant potential electrolytic hydrogenation for 4 hours at different potentials.
Detailed Description
The invention is described in further detail below with reference to examples and figures:
a hydrodeoxygenation method for biological oil comprises the steps of placing biological oil into an H-type electrolytic tank to load Pt/CeO 2 Carrying out constant potential electrochemical hydrodeoxygenation on the catalyst and carrying out electrolysis operation by adopting negative potential;
the anode chamber and the cathode chamber of the H-shaped electrolytic tank are isolated by adopting a Nafion117 membrane, the anode of the H-shaped electrolytic tank adopts a platinum net, the cathode adopts carbon paper as a carrier, and Pt/CeO is loaded 2 a/C catalyst, which uses Ag/AgCl electrode as reference electrode;
the electrolyte in the cathode chamber of the H-type electrolytic tank comprises 47.5wt% of isopropanol, 47.5wt% of deionized water and 5wt% of acetic acid;
the electrolyte in the anode chamber of the H-type electrolytic tank is 1mol/LKOH solution taking 10 weight percent of methanol and 90 weight percent of deionized water as solvents.
The biological oil comprises unsaturated oxygen-containing compounds such as phenol, methylphenol, dimethylphenol, furfural and the like.
The Pt/CeO 2 The preparation steps of the catalyst comprise:
s1, a proper amount of H 2 PtCl 6 ·6H 2 O solution, glycol, ce (NO) 3 ) 3 ·6H 2 O, vulcanXC-72 adding into the flask, stirring thoroughly for 30min, and adjusting pH to 13 with 1mol/LKOH solution;
s2, the mixed solution is heated to 130 ℃ and N 2 Refluxing in oil bath for 3h under atmosphere, and cooling to room temperature;
s3, carrying out suction filtration on the solution obtained in the step S2, and transferring the suction filtration into a vacuum oven at 80 ℃ for full drying, thus obtaining the product.
Wherein, the Pt/CeO is preferable 2 3.9. 3.9mMH for the catalyst/C 2 PtCl 6 ·6H 2 O solution, 100mL of ethylene glycol, 51-202mgCe (NO) 3 ) 3 ·6H 2 O and 80-140mgVulcan XC-72 are used as raw materials, wherein 151mgCe (NO) is preferably used 3 ) 3 ·6H 2 O is used as raw material according to Ce (NO 3 ) 3 ·6H 2 The catalyst was designated Pt/10CeO with different amounts of O (51 mg,101mg,151mg,202mg, respectively) 2 /C，Pt/20CeO 2 /C，Pt/30CeO 2 /C，Pt/40CeO 2 /C。
Example 1: benzaldehyde is used as a reactant, and Pt/10CeO is respectively used 2 /C，Pt/20CeO 2 /C，Pt/30CeO 2 /C，Pt/40CeO 2 and/C as a catalyst to test the electrochemical hydrogenation performance of benzaldehyde. The testing method comprises the following steps: respectively carrying out constant potential electrolytic hydrogenation for 4 hours under different potentials, and calculating the average conversion amount of the biological oil per hour.
As shown in FIG. 1, it can be seen from the test that the more negative the potential is, the greater the hydrogenation driving force is, wherein Pt/30CeO 2 The electrochemical catalytic hydrogenation efficiency of/C is highest, and the rule of catalyzing benzaldehyde hydrogenation rate is as follows for catalysts with different ceria contents: as the ceria loading increases, the benzaldehyde hydrogenation rate tends to increase and decrease, at Pt/30CeO 2 The highest hydroconversion rate under/C catalytic hydrogenation indicates that the addition of an appropriate amount of ceria has the effect of improving Pt catalytic efficiency.
Example 2: pt/30CeO according to the above steps 2 and/C is used as a catalyst to test the electrochemical hydrogenation performance of benzaldehyde, furfural, phenol and lactic acid respectively. The testing method comprises the following steps: respectively carrying out constant potential electrolytic hydrogenation for 4 hours under different potentials, and calculating the average conversion amount of the biological oil per hour.
As shown in fig. 2, it can be seen from the test that the more negative the potential is, the greater the hydrogenation driving force is, wherein benzaldehyde and furfural have higher electrochemical hydrogenation efficiency. For the four reactants, the initial potential of hydrogenation is at-0.7V, the hydrogenation efficiency of benzaldehyde gradually rises along with the negative potential shift, and when the potential shifts to-1.5V, the hydrogenation conversion reaches 5.28 mmol.g -1 cat ·h -1 When the potential reaches-1.5V, the hydrogenation conversion amount of the furfural reaches 3.89 mmol.g -1 cat ·h -1 The hydrogenation response of phenol to the system is low, and the maximum conversion is 1.59 mmol.g -1 cat ·h -1 For lactic acid, essentially no hydrogenation reaction occurs under this system.
Finally, it should be noted that the above description is only a preferred embodiment of the present invention, and that many similar changes can be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (2)
1. A method for hydrodeoxygenation of biological oil, characterized by: placing biological oil into H-type electrolytic tank to load Pt/CeO 2 Carrying out potentiostatic electrochemical hydrodeoxygenation on the catalyst;
the anode chamber and the cathode chamber of the H-shaped electrolytic tank are isolated by adopting a Nafion117 membrane, the anode of the H-shaped electrolytic tank adopts a platinum net, the cathode adopts carbon paper as a carrier, and Pt/CeO is loaded 2 a/C catalyst, which uses Ag/AgCl electrode as reference electrode;
the electrolyte in the cathode chamber of the H-type electrolytic tank comprises 47.5wt% of isopropanol, 47.5wt% of deionized water and 5wt% of acetic acid;
the electrolyte in the anode chamber of the H-type electrolytic tank is 1mol/LKOH solution taking 10 weight percent of methanol and 90 weight percent of deionized water as solvents;
the biological oil comprises phenol, methylphenol, dimethylphenol and furfural unsaturated oxygen-containing compounds;
the Pt/CeO 2 The preparation steps of the catalyst comprise:
s1, a proper amount of H 2 PtCl 6 ·6H 2 O solution, glycol, ce (NO) 3 ) 3 ·6H 2 O, vulcanXC-72 adding into the flask, stirring thoroughly for 30min, and adjusting pH to 13 with 1mol/LKOH solution;
s2, the mixed solution is heated to 130 ℃ and N 2 Refluxing in oil bath for 3h under atmosphere, and cooling to room temperature;
s3, carrying out suction filtration on the solution obtained in the step S2, and transferring the suction filtration into a vacuum oven at 80 ℃ for full drying, thus obtaining the product;
carrying out electrolysis operation by adopting negative potential, wherein the negative potential is-0.7V to-1.5V;
the Pt/CeO 2 3.9. 3.9mMH for the catalyst/C 2 PtCl 6 ·6H 2 O solution, 100mL of ethylene glycol, 51-202mgCe (NO) 3 ) 3 ·6H 2 O and 80-140mgVulcanXC-72 are used as raw materials.
2. A method of hydrodeoxygenation of a bio-oil according to claim 1, wherein: the Pt/CeO 2 The catalyst/C adopts 151mgCe (NO) 3 ) 3 ·6H 2 O is used as a raw material.
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| CN108660479B (en) * | 2018-04-29 | 2019-12-10 | 浙江工业大学 | Method for preparing KA oil and derivatives thereof through electrocatalytic hydrogenation of lignin-based phenolic compounds |
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