CN111909736B - Electrochemical upgrading method for bio-oil - Google Patents
Electrochemical upgrading method for bio-oil Download PDFInfo
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Abstract
The invention belongs to the field of biomass energy utilization, and discloses a bio-oil electrochemical upgrading method, which comprises the following steps: (a) Mixing biological oil, an organic solvent and a supporting electrolyte to obtain catholyte; (b) preparing an acid solution as an anolyte; (c) An electrochemical reactor is formed by adopting catholyte and anolyte, the catholyte and the anolyte are separated by 1 or 2 ion exchange membranes, and a current loop can be formed; (d) And after protective gas is introduced to one side of the catholyte, current is introduced through the working electrode and the anode electrode to perform electrochemical reaction, so that the electrochemical upgrading of the bio-oil can be realized. Compared with the prior art, the method can effectively solve the problem that carbon deposition is easily formed in the bio-oil upgrading by a thermochemical method, and can be used for electrochemically upgrading the bio-oil under mild conditions, so that the upgrading can reduce the content of biological oleic acid, aromatic components and heavy components, the bio-oil is suitable for transportation and storage, and the generation of carbon deposition is avoided in the upgrading process.
Description
Technical Field
The invention belongs to the field of biomass energy utilization, and particularly relates to an electrochemical upgrading method for bio-oil.
Background
Bio-oil is the pyrolysis product of biomass and is the only carbon-containing renewable energy source present in liquid form. Compared to biomass, bio-oil has a high energy density, typically up to 10 times the energy density of biomass. The conversion of biomass into bio-oil is a promising low-cost utilization of biomass energy. However, bio-oils currently have no mature industrially applicable or processing technology. The fundamental reason for the difficulty in handling and applying bio-oil is its characteristic physicochemical properties. Bio-oil is complex in composition, high in acid value, high in viscosity and corrosive, which makes it difficult to transport and store on a large scale. The bio-oil has high oxygen content, many heavy components (high molecular weight) and low heat value, which makes it difficult to directly apply the bio-oil to combustion equipment. Therefore, bio-oils must be refined and upgraded to improve fuel properties or to refine high value-added chemicals. At present, the bio-oil upgrading method is mainly based on traditional methods of thermochemical hydrodeoxygenation, catalytic cracking, steam reforming and the like, and the treatment process needs to be carried out in a high-temperature or high-pressure environment. However, the bio-oil has poor thermal stability, is easily coked by heating to form carbon deposition, causes reactor blockage or catalyst inactivation, reduces the upgrading efficiency, and even causes difficult reaction.
In view of the above, the development of a bio-oil quality-improving method under mild conditions (such as normal temperature and normal pressure) would have important application value.
Disclosure of Invention
In view of the above defects or improvement requirements of the prior art, the present invention aims to provide an electrochemical upgrading method for bio-oil, wherein electrochemical treatment adopted by the upgrading method, and specific parameters and conditions adopted by the electrochemical treatment are improved, so that compared with the prior art, the problem that the bio-oil is easy to form carbon deposition in the traditional thermochemical method for upgrading bio-oil can be effectively solved.
In order to achieve the above object, according to the present invention, there is provided a bio-oil electrochemical upgrading method, comprising the steps of:
(a) Mixing biological oil, an organic solvent and a supporting electrolyte to obtain a liquid serving as catholyte for later use; wherein the supporting electrolyte is used to increase conductivity;
(b) Preparing an acid solution with the concentration of 0.2-1.0mol/L as an anolyte for later use;
(c) Adopting the catholyte and the anolyte to construct an electrochemical reactor, inserting a working electrode into the catholyte, inserting an anode electrode into the anolyte, and separating the catholyte and the anolyte through 1 or 2 ion exchange membranes to form a current loop;
(d) After protective gas is introduced into one side of the catholyte, current is introduced through the working electrode and the anode electrode to carry out electrochemical reaction; the electrochemical reaction is carried out for 2-8h under the condition of 50-200mA current, so that the electrochemical upgrading of the bio-oil can be realized.
As a further preferable mode of the present invention, in the step (a), the bio-oil is directly obtained by pyrolyzing agricultural and forestry waste biomass at a high temperature of not less than 500 ℃ and then condensing;
preferably, the agricultural and forestry waste biomass is rice hulls, straws, edible fungus matrixes, tree branches or barks.
As a further preferred of the present invention, in the step (a), the organic solvent is an alcohol solvent, preferably one or more of methanol, ethanol, n-propanol or isopropanol; the mass ratio of the biological oil component to the alcohol solvent component in the catholyte is 9-4.
As a further preferred aspect of the present invention, in the step (a), the supporting electrolyte is lithium chloride (LiCl), tetrabutyl hexafluorophosphate (Bu) 4 NPF 6 ) Or tetrabutyltetrafluoroborate (Bu) 4 NBF 4 ) And the concentration of the supporting electrolyte in the catholyte is 0.1-0.2mol/L.
As a further preferred aspect of the present invention, in the step (b), the acid is sulfuric acid, hydrochloric acid, perchloric acid or phosphoric acid.
As a further preferred aspect of the present invention, in the step (c), the electrochemical reactor is based on an H-type electrolytic cell, and the catholyte and the anolyte are respectively located at two sides of the H-type electrolytic cell and separated by a cation exchange membrane.
As a further preference of the present invention, in the step (c), the electrochemical reactor is based on a single-membrane two-compartment electrolytic cell or a two-membrane three-compartment electrolytic cell;
when the electrolytic cell is based on a single-membrane double-chamber electrolytic cell, the catholyte and the anolyte are respectively positioned at two sides of the single-membrane double-chamber electrolytic cell, and the middles of the catholyte and the anolyte are separated by a cation exchange membrane;
when the electrolytic cell is based on the double-membrane three-chamber electrolytic cell, the catholyte and the anolyte are respectively positioned at two sides of the double-membrane three-chamber electrolytic cell and are connected through the middle chamber; the catholyte is separated from the intermediate chamber by an anion exchange membrane, and the anolyte is separated from the intermediate chamber by a cation exchange membrane.
In a further preferred aspect of the present invention, in the step (c), the anode electrode is a platinum electrode, a ruthenium electrode, a palladium electrode, or a nickel electrode;
the working electrode is a metal material electrode or a metal material modified electrode; wherein the metal material electrode is selected from a nickel electrode, a ruthenium electrode, a palladium electrode, a platinum electrode, a copper electrode, a gold electrode and a stainless steel electrode; the metal material modified electrode is obtained by processing a substrate material by using a metal material, wherein the substrate material is selected from carbon fiber cloth, activated carbon cloth, glass carbon fiber paper, carbon paper, a graphite sheet and foamed nickel, the metal material is salt of iron, nickel, ruthenium, palladium or platinum element, and Fe (NO) is preferred 3 ) 3 、Ni(NO 3 ) 2 、Ru(NH 3 ) 6 Cl 3 、Pd(NO 3 ) 2 Or H 2 PtCl 6 。
In a further preferred embodiment of the present invention, the metal material modified electrode is obtained by a dipping method, a plating method, or a hydrothermal method.
As a further preferred aspect of the present invention, in the step (d), the protective gas is nitrogen or an inert gas; preferably, the inert gas is argon or helium.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the existing bio-oil upgrading technology, the method has the greatest advantages that the method aims at all components of bio-oil, the bio-oil is not required to be separated in advance, the process is simple, the carbon components in the bio-oil are kept to the greatest extent, and the method is convenient for further processing and utilization after upgrading.
(2) According to the invention, under the action of electric energy, the purpose of primarily upgrading the bio-oil under mild conditions is realized through the breakage of C-O chemical bonds in the bio-oil component molecules, the hydrogenation of benzene rings and the in-situ coupling of acid-alcohol esterification reaction, so that the content of bio-oleic acid, the content of aromatic components and the content of heavy components are reduced, and the bio-oil is more suitable for transportation and storage. The biological oil sample can be effectively dissolved by adopting the organic solvent, and the viscosity of the biological oil sample is reduced, so that the biological oil sample is suitable for the electrolytic cell; meanwhile, the alcohol solvent is preferably used as the organic solvent in the invention, because the alcohol is one of the main components of the bio-oil, the viscosity of the bio-oil is reduced after the bio-oil is added, but the components are not influenced too much, and the bio-oil can be directly utilized after being upgraded.
(3) The invention has mild reaction conditions, the whole electrochemical treatment process is carried out at normal temperature (such as 20-25 ℃, certainly at other temperatures of 20-60 ℃) and normal pressure (namely, one standard atmospheric pressure), the process operation is simple, no coking and carbon deposition exist in the reaction process, the reaction start and stop are rapid, the reaction conditions can be accurately controlled, and the discontinuous or continuous reaction can be realized. The method is preferably carried out at 20-60 ℃ to be suitable for the electrochemical upgrading of the bio-oil, so that the negative effects that the reactivity of components in the bio-oil is low and the upgrading efficiency is low when the temperature is lower than 20 ℃, and side reactions such as hydrogen evolution and the like begin to be active and the upgrading efficiency is reduced when the temperature is higher than 60 ℃ can be avoided (certainly, the too high temperature can also cause the evaporation of alcohol components or solvents to cause the deterioration of the fluidity of the bio-oil and influence the reaction process).
Biological oils have the characteristics of high viscosity, low conductivity, and low solubility in supporting electrolytes, making them unsuitable for electrochemical processes. The invention adopts organic solvent (especially alcohol solvent), on one hand, the biological oil sample can be effectively dissolved, and the viscosity of the biological oil sample can be reduced, so that the biological oil sample is suitable for the electrolytic cell. On the other hand, by using a supporting electrolyte having a high solubility in these organic solvents in combination, and preferably making the concentration of the supporting electrolyte in the catholyte to be 0.1 to 0.2mol/L, it is possible to overcome the disadvantages of low solubility of the supporting electrolyte in the bio-oil and low conductivity of the bio-oil and to improve the conductivity of the bio-oil. In addition, the invention preferably adopts an alcohol solvent as the organic solvent, the type of the alcohol solvent can be particularly determined according to alcohol components contained in the bio-oil, and the alcohol solvent contained in the bio-oil is selectively added, so that the influence on the components of the bio-oil can be reduced to the greatest extent, and the bio-oil after being upgraded can be further utilized conveniently. Taking an organic solvent as an alcohol solvent as an example, the ratio of the bio-oil to the alcohol solvent in the invention is preferably 9-1, and the method is very suitable for the electrochemical upgrading of the bio-oil, and can avoid the problems that when the ratio of the bio-oil to the alcohol solvent is too low, the alcohol solvent is too much, the alcohol solvent is volatilized to cause the loss of organic components in the bio-oil, and the upgrading effect is influenced; and when the ratio of the biological oil to the alcohol solvent is too high, the fluidity of the biological oil is insufficient, the electrochemical quality improvement is not facilitated, and meanwhile, the negative effects of saturated adsorption-state reaction substance sites on the surface of the electrode, low reaction efficiency and the like are caused due to too high biological oil concentration.
Aromatic components in the bio-oil are easy to generate oxidation reaction at the anode and polymerize in the electrochemical treatment process, and carbon deposition is generated on the surface of the electrode. The invention adopts the form of an ion exchange membrane to ensure that the bio-oil only participates in the reaction at one side of the cathode. On one hand, the polymerized carbon deposition of the bio-oil at the anode can be avoided, on the other hand, the acid in the bio-oil can be effectively removed, and the corrosivity of the bio-oil is reduced. The acid in the bio-oil can be separated by adopting a three-chamber and two-membrane mode, and the acid can be used as a byproduct of the method after collection.
The current range of the invention is 50-200mA, which is a current interval suitable for the electrochemical upgrading of the bio-oil. The current is directly related to the reaction rate, which in turn affects the upgrading efficiency. The current is lower than 50mA, the quantity of electrons, protons and adsorbed reactants participating in the reaction on the surface of the electrode is insufficient, and the biological oil quality improvement efficiency is not high; the current is higher than 200mA, the adsorption state reaction substance sites on the surface of the electrode are saturated, the increase of the current does not bring the increase of the upgrading reaction strength, but leads the increase of the side reaction strength such as hydrogen evolution and the like, and reduces the upgrading efficiency of the bio-oil, therefore, the invention adopts the electrochemical reaction under the current condition of 50-200 mA.
Drawings
FIG. 1 is a graph of the trend of acetic acid content in upgraded bio-oil over time (as measured by GC-MS in GC-MS) in example 1 of the present invention.
FIG. 2 is a graph of the time dependence of the aromatic content of the upgraded bio-oil of example 1 of the present invention (as measured by UV fluorescence spectroscopy).
FIG. 3 is a comparison graph of mass distribution change of bio-oil molecules before and after upgrading (detected by Fourier transform ion cyclotron resonance mass spectrometer FT-ICR MS) in example 1 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The method for electrochemically upgrading the bio-oil can comprise the following steps:
(a) Firstly, adding supporting electrolyte into an alcohol solvent, mixing bio-oil with the alcohol solvent, and taking the mixed liquid as catholyte for later use; the addition of the supporting electrolyte can improve the conductivity of the bio-oil;
(b) Preparing an acid solution with the concentration of 0.2-1.0mol/L as an anolyte for later use (the acid solution is a protic solvent and can dissociate out protic hydrogen in the solution, and the protic hydrogen enters catholyte through a cation exchange membrane and is adsorbed on the surface of a cathode so as to provide a hydrogen source for hydrogenation of bio-oil);
(c) Assembling the electrochemical reactor: preparing an H-shaped electrolytic cell, separating the middle of the H-shaped electrolytic cell by a cation exchange membrane, respectively filling catholyte and anolyte into two sides of the H-shaped electrolytic cell, inserting a working electrode into the catholyte, inserting a platinum sheet electrode into the anolyte, and connecting the electrodes by using a constant current instrument;
(d) And after introducing nitrogen or inert gas into one side of the catholyte, turning on a power supply, and reacting for 2-8 hours under the condition of 50-200mA current to realize the electrochemical quality improvement of the bio-oil.
In addition, in the step (a), the concentration of the supporting electrolyte in the catholyte is 0.1-0.2mol/L, and the bio-oil and the alcohol solvent are mixed according to the mass ratio of 9-4.
The H-type electrolytic cell may be a single membrane electrolytic cell or a double membrane electrolytic cell. When a single-membrane electrolytic cell is adopted, catholyte and anolyte are respectively filled into two sides of the H-shaped electrolytic cell, and the middle of the H-shaped electrolytic cell is separated by a cation exchange membrane; when a double-membrane three-chamber electrolytic cell is adopted, an anion exchange membrane is adopted on one side of catholyte, and a cation exchange membrane is adopted on one side of anolyte. The cation exchange membrane and the anion exchange membrane can be made of functional materials known in the prior art, for example, the cation exchange membrane can be made of Nafion-1035, nafion-115 or Nafion-117 membrane (taking the cation exchange membrane as an example, the cation exchange membrane allows the proton hydrogen in the anolyte to pass through into the catholyte, and effectively separates the anolyte from the catholyte).
The following are specific examples:
example 1
The embodiment specifically comprises the following steps:
(a) Firstly, adding 0.1mol/L LiCl supporting electrolyte into methanol, mixing bio-oil and methanol according to the mass ratio of 4;
(b) Preparing a dilute sulfuric acid solution with the concentration of 0.5mol/L as anolyte for later use;
(c) Assembling the electrochemical reactor: preparing an H-shaped electrolytic cell, separating the middle of the H-shaped electrolytic cell by a Nafion-117 cation exchange membrane, respectively filling catholyte and anolyte into two sides of the H-shaped electrolytic cell, inserting a platinum sheet electrode into the catholyte, inserting a platinum sheet electrode into the anolyte, and connecting the electrodes by using a constant current instrument;
(d) And introducing nitrogen into one side of the catholyte for 15min, then turning on a power supply, and carrying out constant current of 50mA, reaction temperature of 20 ℃ and reaction time of 8h to realize quality improvement of the bio-oil. The change of acetic acid content in the bio-oil with time, the change of aromatic component content with time and the change of molecular mass before and after upgrading are respectively shown in figure 1, figure 2 and figure 3.
FIG. 1 is a graph showing the trend of acetic acid content in the process of the bio-oil electrochemical upgrading reaction along with time (sampling interval is 2 h), the acetic acid content is gradually reduced along with the reaction, and the acetic acid content is reduced by 54.5% after 8 h.
FIG. 2 is a graph showing the time-varying trend of the aromatic content during the electrochemical upgrading reaction of bio-oil (sampling interval 2 h), the aromatic content gradually decreases as the reaction proceeds, and the aromatic content decreases by 67.9% after 8 h.
FIG. 3 is the molecular mass change of bio-oil before upgrading and after 8h upgrading, and it can be seen that for each molecular mass distribution interval, the abundance is reduced, which shows that the molecular mass of bio-oil after upgrading is reduced and the content of heavy components is reduced.
Example 2
The concentration of the anolyte dilute sulfuric acid used in this example was 0.2mol/L, and the other conditions were the same as in example 1. After 8h of quality improvement, the acetic acid content of the bio-oil is reduced by 26.7%, the aromatic component content is reduced by 34.1%, and the molecular quality of the bio-oil is reduced.
Example 3
The embodiment specifically comprises the following steps:
(a) First, 0.1mol/L Bu was added to methanol 4 NBF 4 Supporting electrolyte, mixing the bio-oil and methanol according to the mass ratio of 6;
(b) Preparing a dilute sulfuric acid solution with the concentration of 0.5mol/L as anolyte for later use;
(c) Assembling the electrochemical reactor: preparing an H-shaped electrolytic cell, separating the middle of the H-shaped electrolytic cell by a Nafion-117 cation exchange membrane, respectively filling catholyte and anolyte into two sides of the H-shaped electrolytic cell, inserting a carbon-based ruthenium electrode into the catholyte, inserting a platinum sheet electrode into the anolyte, and connecting the electrodes by using a constant current meter; the carbon-based ruthenium electrode is prepared by adopting an electroplating method (the specific process of the electroplating method can be directly referred to related prior art).
(d) And after nitrogen is introduced into one side of the catholyte for 15min, a power supply is turned on, the constant current is 100mA, the reaction temperature is 40 ℃, the reaction time is 2h, the bio-oil quality improvement is realized, the acetic acid content of the bio-oil is reduced by 18.3%, the aromatic component content is reduced by 46.0%, and the molecular quality of the bio-oil is reduced.
Example 4
The embodiment specifically comprises the following steps:
(a) Firstly, adding 0.1mol/L LiCl supporting electrolyte into methanol, mixing bio-oil and methanol according to the mass ratio of 9;
(b) Preparing a dilute hydrochloric acid solution with the concentration of 0.5mol/L as anolyte for later use;
(c) Assembling the electrochemical reactor: preparing an H-shaped electrolytic cell, separating the middle of the H-shaped electrolytic cell by a Nafion-117 cation exchange membrane, respectively filling catholyte and anolyte into two sides of the H-shaped electrolytic cell, inserting a Ni-Fe modified foam nickel electrode into the catholyte, inserting a platinum sheet electrode into the anolyte, and connecting the electrodes by a constant current meter; the Ni-Fe modified foam nickel electrode is prepared by adopting an impregnation method (the specific process of the impregnation method can be directly referred to related prior art).
(d) After nitrogen is introduced into one side of the catholyte for 15min, a power supply is turned on, the constant current is 200mA, the reaction temperature is 60 ℃, the reaction time is 2h, the bio-oil quality improvement is realized, the acetic acid content of the bio-oil is reduced by 37.5%, the aromatic component content is reduced by 65.7%, and the molecular quality of the bio-oil is reduced.
Example 5
The embodiment specifically comprises the following steps:
(a) Firstly, adding 0.1mol/L LiCl supporting electrolyte into methanol, mixing bio-oil and methanol according to the mass ratio of 9;
(b) Preparing a dilute hydrochloric acid solution with the concentration of 0.5mol/L as an anolyte for later use;
(c) Assembling the electrochemical reactor: preparing a double-membrane three-chamber electrolytic cell, wherein a Nafion-117 cation exchange membrane is arranged on one side of anolyte, an anion exchange membrane is adopted as catholyte, deionized water is filled in a middle chamber, the catholyte and the anolyte are respectively filled into two sides of an H-shaped electrolytic cell, a nickel electrode is inserted into the catholyte, a platinum sheet electrode is inserted into the anolyte, and the electrodes are connected by a constant current instrument.
(d) And after nitrogen is introduced into one side of the catholyte for 15min, turning on a power supply, keeping the constant current at 200mA, keeping the reaction temperature at 40 ℃, and keeping the reaction time for 6h to realize the quality improvement of the bio-oil, reduce the acetic acid content of the bio-oil by 43.2 percent, reduce the aromatic component content by 66.3 percent, and reduce the molecular mass of the bio-oil. The acidic substances in the bio-oil are separated into the intermediate chamber.
Example 6
The embodiment specifically comprises the following steps:
(a) Firstly, adding 0.2mol/L LiCl supporting electrolyte into methanol, mixing bio-oil and methanol according to a mass ratio of 4;
(b) Preparing a dilute sulfuric acid solution with the concentration of 1.0mol/L as an anolyte for later use;
(c) Assembling the electrochemical reactor: preparing an H-shaped electrolytic cell, separating the middle of the H-shaped electrolytic cell by a Nafion-117 cation exchange membrane, respectively filling catholyte and anolyte into two sides of the H-shaped electrolytic cell, inserting a platinum sheet electrode into the catholyte, inserting a platinum sheet electrode into the anolyte, and connecting the electrodes by using a constant current instrument;
(d) And after nitrogen is introduced into one side of the catholyte for 15min, a power supply is turned on, the constant current is 50mA, the reaction temperature is 20 ℃, the reaction time is 8h, the bio-oil quality improvement is realized, the acetic acid content of the bio-oil is reduced by 71.7%, the aromatic component content is reduced by 63.4%, and the molecular quality of the bio-oil is reduced.
The bio-oil used in the above embodiment may be obtained directly by pyrolyzing agricultural and forestry waste biomass such as rice hulls, straws, edible fungus matrixes, tree branches or barks at a high temperature of 500 ℃ and then condensing (of course, the pyrolysis temperature may also be higher than 500 ℃).
The environmental temperature of the above examples was 20 to 60 ℃ (of course, the temperature may be other temperatures as long as the reaction system still satisfies the solution system required for the electrochemical reaction due to the influence of the temperature on the reaction system), and the atmospheric pressure was normal pressure.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The bio-oil electrochemical upgrading method is characterized by comprising the following steps:
(a) Mixing biological oil, an organic solvent and a supporting electrolyte to obtain a liquid serving as catholyte for later use; wherein the supporting electrolyte is used to increase conductivity; the organic solvent is an alcohol solvent, and the mass ratio of the biological oil component to the alcohol solvent component in the catholyte is 9-4; the type of the alcohol solvent is determined according to the alcohol component contained in the biological oil, and the alcohol solvent contained in the biological oil is selected and added;
(b) Preparing an acid solution with the concentration of 0.2-1.0mol/L as an anolyte for later use;
(c) An electrochemical reactor is formed by adopting the catholyte and the anolyte, a working electrode is inserted into the catholyte, an anode electrode is inserted into the anolyte, and the catholyte and the anolyte are separated by 2 ion exchange membranes and can form a current loop;
the electrochemical reactor is based on a double-membrane three-chamber electrolyzer; wherein, the catholyte and the anolyte are respectively positioned at two sides of the double-membrane three-chamber electrolytic cell and are connected through an intermediate chamber; the catholyte is separated from the intermediate chamber through an anion exchange membrane, and the anolyte is separated from the intermediate chamber through a cation exchange membrane;
(d) After protective gas is introduced into one side of the catholyte, current is introduced through the working electrode and the anode electrode to carry out electrochemical reaction; the electrochemical reaction is carried out for 2-8h at the temperature of 20-60 ℃ under the current condition of 50-200mA, and in the electrochemical reaction process, the C-O chemical bond breakage, benzene ring hydrogenation and acid-alcohol esterification reaction in the bio-oil component molecule can occur, so that the bio-oil electrochemical quality improvement can be realized; wherein the protective gas is an inert gas.
2. The bio-oil electrochemical upgrading method according to claim 1, wherein in the step (a), the bio-oil is directly obtained by condensing agriculture and forestry waste biomass after pyrolysis at a high temperature of not less than 500 ℃;
the agricultural and forestry waste biomass is rice husk, straw, edible fungus matrix, tree branches or bark.
3. The bio-oil electrochemical upgrading method according to claim 1, wherein in the step (a), the organic solvent is one or more of methanol, ethanol, n-propanol or isopropanol.
4. The method for electrochemically upgrading bio-oil according to claim 1, wherein in step (a), the supporting electrolyte is LiCl or Bu 4 NPF 6 Or Bu 4 NBF 4 And the concentration of the supporting electrolyte in the catholyte is 0.1-0.2mol/L.
5. The bio-oil electrochemical upgrading method according to claim 1, wherein in step (b), the acid is sulfuric acid, hydrochloric acid, perchloric acid or phosphoric acid.
6. The bio-oil electrochemical upgrading method according to claim 1, wherein in the step (c), the electrochemical reactor is based on an H-type electrolytic cell, and the catholyte and the anolyte are respectively located at two sides of the H-type electrolytic cell and separated by a cation exchange membrane in the middle.
7. The bio-oil electrochemical upgrading method according to claim 1, wherein in the step (c), the anode electrode is a platinum electrode, a ruthenium electrode, a palladium electrode, or a nickel electrode;
the working electrode is a metal material electrode or a metal material modified electrode; wherein the metal material electrode is selected from a nickel electrode, a ruthenium electrode, a palladium electrode, a platinum electrode, a copper electrode, a gold electrode and a stainless steel electrode; the metal material modified electrode is obtained by processing a substrate material by using a metal material, wherein the substrate material is selected from carbon fiber cloth, activated carbon cloth, glass carbon fiber paper, carbon paper, a graphite sheet and foamed nickel, and the metal material is salt of iron, nickel, ruthenium, palladium or platinum elements.
8. The bio-oil electrochemical upgrading method of claim 7, wherein the metal material is Fe (NO) 3 ) 3 、Ni(NO 3 ) 2 、Ru(NH 3 ) 6 Cl 3 、Pd(NO 3 ) 2 Or H 2 PtCl 6 。
9. The bio-oil electrochemical upgrading method according to claim 7, wherein the metal material modified electrode is obtained by treatment through a dipping method, a plating method or a hydrothermal method.
10. The bio-oil electrochemical upgrading method of claim 1, wherein the inert gas is nitrogen, argon or helium.
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| CN112779089A (en) * | 2020-12-22 | 2021-05-11 | 华中科技大学 | System and method for in-situ removal of electrode coke in biomass pyrolysis oil electrolysis upgrading process |
| CN113713734B (en) * | 2021-08-13 | 2022-09-27 | 华中科技大学 | Method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil |
| CN113717746B (en) * | 2021-09-30 | 2023-06-30 | 云南电网有限责任公司电力科学研究院 | Hydrodeoxygenation method for biological oil |
| CN115404126B (en) * | 2022-09-09 | 2024-03-19 | 华中科技大学 | Method for improving organic acid in biomass pyrolysis oil by using carbon dioxide |
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