WO2022021909A1 - Bio-oil electrochemical upgrading method and bio-oil electrochemical hydrogenation upgrading device - Google Patents

Abstract

The present invention relates to the field of biomass energy utilization. Disclosed are a bio-oil electrochemical upgrading method and a bio-oil electrochemical hydrogenation upgrading device. The bio-oil electrochemical upgrading method comprises the following steps: (a) mixing bio-oil, an organic solvent, and a supporting electrolyte to obtain a catholyte; (b) preparing an acid solution as an anolyte; (c) constructing an electrochemical reactor by using the catholyte and the anolyte, and separating the catholyte from the anolyte by means of one or two ion exchange membranes, thus forming a current loop; and (d) introducing a protective gas into one side of the catholyte, and then introducing current by means of a working electrode and an anode electrode to perform electrochemical reaction, thereby implementing the electrochemical upgrading of the bio-oil. According to the present invention, the problem that carbon deposition is easily formed when the bio-oil is upgraded by a thermochemical method can be effectively solved, the bio-oil is subjected to electrochemical upgrading under mild conditions, and the content of bio-oleic acid, the content of aromatic components and the content of heavy components can be reduced by upgrading, so that the bio-oil is suitable for transportation and storage.

Description

A kind of biological oil electrochemical upgrading method and biological oil electrochemical hydrogenation upgrading device 【Technical field】

The invention belongs to the field of biomass energy utilization, and more particularly relates to a method for electrochemical upgrading of biological oil and an electrochemical hydrogenation upgrading device for biological oil.

【Background technique】

Bio-oil is the pyrolysis product of biomass and is the only carbon-containing renewable energy source in liquid form. Compared with biomass, bio-oil has a high energy density, usually up to 10 times the energy density of biomass. Converting biomass to bio-oil is a promising low-cost utilization of biomass energy. However, there is still no mature industrialized application or processing technology for bio-oil. The fundamental reason for the difficult handling and application of bio-oil is its unique physical and chemical properties. Bio-oil has complex composition, high acid value, high viscosity and corrosiveness, which make it difficult to transport and store it on a large scale. Bio-oil has high oxygen content, many heavy components (high molecular weight), and low calorific value, which makes it difficult to directly apply to combustion equipment. Therefore, bio-oil must be refined to improve fuel properties or to refine high value-added chemicals. At present, the upgrading methods of bio-oil are mainly based on traditional methods such as thermochemical hydrodeoxygenation, catalytic cracking, steam reforming, etc. The treatment process needs to be carried out in a high temperature or high pressure environment. However, the thermal stability of bio-oil is poor, and it is easy to coke to form carbon deposits when heated, which causes the blockage of the reactor or the deactivation of the catalyst, reduces the upgrading efficiency, and even makes the reaction difficult to carry out.

In view of the above situation, the development of a bio-oil upgrading method under mild conditions (such as normal temperature and normal pressure) will have important application value.

At the same time, although the rapid pyrolysis of biomass to produce bio-oil, fuel gas, bio-char, etc. has become an effective way to utilize biomass resources, bio-oil is due to its high viscosity, high moisture, high oxygen content, corrosiveness and Due to characteristics such as chemical instability, direct application is limited. Therefore, bio-oil should be hydroupgraded before it can be used to produce liquid fuels. The traditional hydro-upgrading process is carried out at high temperature. However, bio-oil is easy to polymerize when heated. At high temperature, it will polymerize to form coke due to its thermal instability, which will block the catalyst active site and reactor, and affect the stability of the upgrading process. life. In view of the above situation, it is also necessary to design an electrochemical-based bio-oil hydro-upgrading device under mild conditions.

[Content of the invention]

In view of the above defects or improvement needs of the prior art, the purpose of the present invention is to provide a bio-oil electrochemical upgrading method and a bio-oil electrochemical hydrogenation and upgrading device, wherein in terms of the bio-oil electrochemical upgrading method, by The electrochemical treatment used in the upgrading method, as well as the specific parameters and conditions used in the electrochemical treatment, are improved, which can effectively solve the problem that the traditional thermochemical method of upgrading bio-oil is easy to form carbon deposits compared with the prior art. The invention can carry out electrochemical upgrading of bio-oil under mild conditions (such as normal temperature and normal pressure), and the upgrading can reduce the content of bio-oleic acid, aromatic components and heavy components, so that the bio-oil is suitable for transportation and storage , and at the same time avoid the generation of carbon deposits in the upgrading process; and for the bio-oil electrochemical hydrogenation and upgrading device, by improving the structure of each component of the device and their arrangement, compared with the prior art, The electrochemical hydrogenation and upgrading of bio-oil at a constant temperature can be realized, and the on-line sampling of bio-oil on the electrode surface can be further realized through the structural design of the cathode chamber.

In order to achieve the above object, according to one aspect of the present invention, a method for electrochemical upgrading of biological oil is provided, which is characterized in that, comprising the following steps:

(a) mixing the bio-oil, the organic solvent and the supporting electrolyte, and the liquid obtained by mixing is used as the catholyte for standby use; wherein, the supporting electrolyte is used to improve the electrical conductivity;

(b) preparing an acid solution with a concentration of 0.2-1.0 mol/L as the anolyte for standby use;

(c) using the catholyte and the anolyte to form an electrochemical reactor, inserting a working electrode into the catholyte, inserting an anode electrode into the anolyte, and passing between the catholyte and the anolyte 1 or 2 ion exchange membranes are separated and can form a current loop;

(d) after the protective gas is introduced into the catholyte side, electric current is passed through the working electrode and the anode electrode to carry out an electrochemical reaction; the electrochemical reaction is a reaction under the condition of 50-200mA current 2-8h, thus the electrochemical upgrading of bio-oil can be realized.

As a further preference of the present invention, in the step (a), the bio-oil is directly obtained by condensation after pyrolysis of agricultural and forestry waste biomass at a high temperature of not less than 500°C;

Preferably, the agricultural and forestry waste biomass is rice husk, straw, edible fungus substrate, tree branches or bark.

As a further preference 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 oil component to the alcohol solvent component satisfies 9:1-4:1.

As a further preference of the present invention, in the step (a), the supporting electrolyte is lithium chloride (LiCl), tetrabutyl hexafluorophosphate (Bu ₄ NPF ₆ ) or tetrabutyl tetrafluoroborate ( Bu ₄ NBF ₄ ), the concentration of the supporting electrolyte in the catholyte is 0.1-0.2 mol/L.

As a further preference of the present invention, in the step (b), the acid is sulfuric acid, hydrochloric acid, perchloric acid or phosphoric acid.

As a further preference of the present invention, in the step (c), the electrochemical reactor is based on an H-type electrolytic cell, the catholyte and the anolyte are respectively located on both sides of the H-type electrolytic cell, and the middle passes through the H-type electrolytic cell. 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-chamber electrolysis cell or a double-membrane three-chamber electrolysis cell;

When based on a single-membrane double-chamber electrolysis cell, the catholyte and the anolyte are located on both sides of the single-membrane double-chamber electrolysis cell, and the middle is separated by a cation exchange membrane;

When based on a double-membrane three-chamber electrolysis cell, the catholyte and the anolyte are located on both sides of the double-membrane three-chamber electrolysis cell, respectively, and are connected through an intermediate chamber; the catholyte is separated from the intermediate chamber by an anion exchange membrane, The anolyte is separated from the intermediate chamber by a cation exchange membrane.

As a further preference 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 nickel electrodes, ruthenium electrodes, palladium electrodes, platinum electrodes, copper electrodes, gold electrodes, and stainless steel electrodes; the metal material modified electrodes It is obtained by processing a base material with a metal material. The base material is selected from carbon fiber cloth, activated carbon cloth, glass carbon fiber paper, carbon paper, graphite sheet, and nickel foam. The metal material is iron, nickel, ruthenium, palladium, or platinum. The salt of the element is preferably Fe(NO ₃ ) ₃ , Ni(NO ₃ ) ₂ , Ru(NH ₃ ) ₆ Cl ₃ , Pd(NO ₃ ) ₂ or H ₂ PtCl ₆ .

As a further preference of the present invention, the metal material modified electrode is obtained by dipping, electroplating or hydrothermal treatment.

As a further preference 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.

According to another aspect of the present invention, a bio-oil electrochemical hydro-upgrading device is provided, which is characterized by comprising an electrolysis unit, a circulation unit and a heating unit, wherein,

The electrolysis unit comprises an anode chamber (1) and a cathode chamber (6), the anode chamber (1) and the cathode chamber (6) are located in a relatively sealed space composed of acid-resistant materials, and both pass through a proton exchange membrane (3) Interphase; wherein, the anode chamber (1) is used for accommodating anolyte, and the cathode chamber (6) is used for accommodating bio-oil; the electrolysis unit can pass the anode electrode (2) and the cathode electrode to all The anode chamber (1) and the cathode chamber (6) provide direct current, so that the bio-oil in the cathode chamber (6) is electrochemically hydrotreated, so as to realize the upgrading of the bio-oil;

The lower part of the anode chamber (1) and the cathode chamber (6) are provided with an electrolyte inlet (9), and the upper part is provided with an electrolyte outlet (10); the circulation unit is located outside the electrolysis unit, It includes a bio-oil circulation unit and an anolyte circulation unit; wherein, the electrolyte inlet (9) of the cathode chamber (6) is connected with the electrolyte outlet (10) through the bio-oil circulation unit, and a closed circulation loop can be formed; the The electrolyte inlet (9) of the anode chamber (1) is connected with the electrolyte outlet (10) through the anolyte circulation unit, which can form a circulation loop;

The heating unit is used for heating the bio-oil in the cathode chamber (6), so that the bio-oil can be electrochemically hydrotreated under a preset temperature condition.

As a further preference of the present invention, the heating unit is composed of a cathode chamber heating resistance wire, a thermocouple, a temperature controller and a DC power supply, wherein the cathode chamber heating resistance wire is laid on the back of the cathode chamber (6), For being connected with the DC power supply, and the joint for connecting with the DC power supply is reserved outside the cathode chamber (6); the thermocouple is used for biological detection in the cathode chamber (6) The temperature of the oil is detected, and the thermostat is used to control the output power of the DC power supply according to the temperature detected by the thermocouple to change the power of the heating resistance wire in the cathode chamber to control the temperature of the electrolyte in the cathode chamber.

As a further preference of the present invention, the electrochemical hydroprocessing is carried out under catalyst conditions, the cathode electrode is a conductive ring (5), and the conductive ring (5) communicates with the protons through the catalytic electrode (4). The exchange membrane (3) is connected; preferably, the catalytic electrode (4) is an electrode based on activated carbon cloth or carbon paper and modified by the catalyst, and the catalyst is Ru, Pt, Pd, Ni, or A salt of Fe element, preferably Ru(NH ₃ ) ₆ Cl ₃ , H ₂ PtCl ₆ , Pd(NO ₃ ) ₂ , Ni(NO ₃ ) ₂ or Fe(NO ₃ ) ₃ ;

The anode electrode is a mesh metal electrode.

As a further preference of the present invention, the electrochemical hydroprocessing is carried out under catalyst conditions, the cathode electrode is a conductive ring (5), and the conductive ring (5) is directly connected to the proton exchange membrane (3) connected, the proton exchange membrane (3) is also coated with the catalyst coating film on the side close to the cathode chamber (6), and the catalyst is a salt of Ru, Pt, Pd, Ni, or Fe element, preferably Ru(NH ₃ ) ₆ Cl ₃ , H ₂ PtCl ₆ , Pd(NO ₃ ) ₂ , Ni(NO ₃ ) ₂ or Fe(NO ₃ ) ₃ ;

The anode electrode is a mesh metal electrode.

As a further preference of the present invention, the bio-oil circulation unit includes a peristaltic pump and a bio-oil storage tank located on the pipeline, and the anolyte circulation unit includes a peristaltic pump and an anolyte storage tank located on the pipeline;

The bio-oil circulation unit is also connected with a cooling unit, and the cooling unit is capable of cooling the bio-oil in the bio-oil circulation unit.

As a further preference of the present invention, the bio-oil electrochemical hydro-upgrading device further includes a sampling unit, the sampling unit includes a capillary sampling tube (11) and a peristaltic pump, the capillary sampling tube (11) is connected to the cathode chamber (6) is connected internally, and is used for sampling the biological oil in the cathode chamber (6) under the action of a peristaltic pump.

As a further preference of the present invention, the sampling unit is also connected with an ultraviolet fluorescence spectrometer and a gas chromatography mass spectrometer, and the ultraviolet fluorescence spectrometer and the gas chromatography mass spectrometer are used for sampling the biological samples obtained by the sampling unit. oil for analysis.

As a further preference of the present invention, the acid-resistant material is polytetrafluoroethylene, and the anode chamber (1) and the cathode chamber (6) are respectively arranged in the grooves of two solid polytetrafluoroethylene blocks with grooves Inside, a relatively sealed space is formed by splicing the two PTFE blocks together with the sealing gasket (7); preferably, the sealing gasket (7) is a PTFE sealing gasket.

As a further preference of the present invention, the electrolyte inlet (9) is located at the bottom of the anode chamber (1) and the cathode chamber (6), respectively, and the electrolyte outlet (10) is located at the anode chamber ( 1) and the lateral top of the cathode chamber (6).

As a further preference of the present invention, a labyrinth turbulence structure is provided at the bottom of both the anode chamber (1) and the cathode chamber (6).

Compared with the prior art, the following beneficial effects can be achieved by the electrochemical upgrading method of bio-oil conceived in the present invention:

(1) Compared with the existing bio-oil upgrading technology, the biggest advantage of the method of the present invention is that the target object of the present invention is the complete components of the bio-oil, the bio-oil does not need to be separated in advance, the process is simple, and the maximum degree of maintenance is maintained. The carbonaceous components in bio-oil are convenient for further processing and utilization after upgrading.

(2) The present invention achieves the purpose of preliminarily upgrading the bio-oil under mild conditions through the cleavage of CO chemical bonds in the molecules of the bio-oil component, the hydrogenation of the benzene ring and the in-situ coupling of the acid-alcohol esterification reaction under the action of electric energy, The content of bio-oleic acid is reduced, the content of aromatic components is reduced, and the content of heavy components is reduced, so that it is more suitable for transportation and storage. The organic solvent used in the present invention can effectively dissolve the bio-oil sample and reduce its viscosity, so that the bio-oil sample is suitable for the electrolytic cell; meanwhile, the present invention preferably uses an alcohol solvent as the organic solvent, because alcohol is the main component of the bio-oil One of the components, the viscosity of the bio-oil is reduced after adding it, but it will not cause too much influence on its components, which is convenient for the direct use of the bio-oil after upgrading.

(3) The reaction conditions of the present invention are mild, and the entire electrochemical treatment process is carried out at normal temperature (such as 20 to 25° C., of course, other temperatures of 20 to 60° C.) and normal pressure (that is, a standard atmospheric pressure). The process is simple, the reaction process is free of coke and carbon deposition, the reaction starts and stops quickly, the reaction conditions can be precisely controlled, and the intermittent or continuous reaction can be realized. The method of the present invention is preferably carried out under the condition of 20-60° C., so as to be suitable for electrochemical upgrading of bio-oil, so as to avoid low reactivity of components in bio-oil when the temperature is lower than 20° C., low upgrading efficiency, and high temperature When the temperature is higher than 60 °C, side reactions such as hydrogen evolution become active, which reduces the negative effects of upgrading efficiency (of course, too high temperature will also cause the evaporation of alcohol components or solvents, resulting in poor fluidity of bio-oil, affecting the reaction process) .

Bio-oil has the characteristics of high viscosity, low conductivity, and low solubility in supporting electrolytes, which make it unsuitable for electrochemical treatment. The present invention adopts organic solvent (especially alcohol solvent), on the one hand, it can effectively dissolve the biological oil sample and reduce its viscosity, so that the biological oil sample is suitable for the electrolytic cell. On the other hand, supporting electrolytes with higher solubility in these organic solvents are used together to preferably make the concentration of supporting electrolytes in the catholyte reach 0.1-0.2 mol/L, which can overcome the low solubility of supporting electrolytes in bio-oil and biological problems. The disadvantage of low oil conductivity, improve the conductivity of bio-oil. In addition, the present invention preferably adopts an alcohol solvent as the organic solvent, and the type of the alcohol solvent can be determined according to the alcohol components contained in the bio-oil. Selecting and adding the alcohol solvent contained in the bio-oil can reduce the impact on the bio-oil to the greatest extent. The influence of the components of the bio-oil itself facilitates the further utilization of the bio-oil after upgrading. Taking the organic solvent as an alcohol solvent as an example, the ratio of bio-oil to alcohol solvent in the present invention is preferably 9:1-4:1, which is very suitable for electrochemical upgrading of bio-oil and can avoid the ratio of bio-oil/alcoholic solvent When the ratio is too low, there will be too much alcohol solvent, and the volatilization of the alcohol solvent will lead to the loss of organic components in the bio-oil, which will affect the upgrading effect; and when the ratio of bio-oil/alcohol solvent is too high, the bio-oil will have insufficient fluidity, which is not conducive to electrochemistry. At the same time, the excessively high concentration of bio-oil leads to the saturation of adsorbed reactive species on the surface of the electrode, resulting in low reaction efficiency and other negative effects.

Aromatic components in bio-oil are easily oxidized and polymerized at the anode during electrochemical treatment, resulting in carbon deposits on the electrode surface. The invention adopts the form of ion exchange membrane to ensure that the biological oil only participates in the reaction on the cathode side. On the one hand, it can avoid carbon deposition in the anode polymerization of bio-oil, and on the other hand, it can effectively remove the acid in the bio-oil and reduce the corrosiveness of the bio-oil. In the form of three-chamber double-membrane, the acid in the bio-oil can also be separated, and after collection, the acid can be used as a by-product of the method.

The current range in the present invention is 50-200 mA, which is a current range suitable for the electrochemical upgrading of bio-oil. The current is directly related to the reaction rate, which in turn affects the upgrading efficiency. When the current is lower than 50mA, the number of electrons, protons and adsorbed reactants participating in the reaction on the surface of the electrode is insufficient, and the efficiency of bio-oil upgrading is not high; when the current is higher than 200mA, the sites of adsorbed reactants on the electrode surface are saturated, and the current will continue to increase. It brings about an increase in the intensity of the upgrading reaction, but leads to an increase in the intensity of side reactions such as hydrogen evolution, which reduces the efficiency of biological oil upgrading. Therefore, the present invention adopts the electrochemical reaction under the condition of 50-200 mA current.

And the bio-oil electrochemical hydrogenation upgrading device in the present invention, compared with the prior art, can also achieve the following beneficial effects:

1) The device for hydrogenation and upgrading of bio-oil using electrochemistry provided by the present invention is simple in structure and easy to operate. It only needs to inject bio-oil and protic solvent into the circulation unit from the liquid storage tank, turn on the peristaltic pump and connect the anode electrode. And the cathode electrode (the cathode electrode can be a catalytic electrode in particular), the hydrogenation upgrading of the bio-oil can be realized. In the device for upgrading bio-oil by electrochemical hydrogenation in the present invention, the anode chamber is the circulation chamber of anolyte (protic solvent), and the cathode chamber is the circulation chamber of catholyte (bio-oil). Methods Hydrogenation to upgrade bio-oil. In particular, the present invention can use a catalytic electrode, for example, a catalyst-modified electrode based on activated carbon cloth or carbon paper. By supporting the catalyst on a carbon-based substrate with a large specific surface area and high porosity, the contact area between the catalyst and the catholyte is increased. residence time, thereby increasing the reaction efficiency.

2) At the same time, the present invention implants a resistance wire on the back of the flow groove of the cathode chamber, which can heat the catholyte and realize the electrochemical hydrogenation of bio-oil at a constant temperature. For different bio-oil feedstocks, the hydrogenation efficiency and target product selectivity can be improved through optimized temperature parameters. That is to say, in the present invention, by setting the heating unit, the catholyte can be heated, so that the catholyte can react in the most suitable temperature range. In addition, the present invention can be equipped with a cooling unit, which can be used together with the heating unit; the cooling unit can be composed of a cooling coil on the pipeline in front of the inlet of the catholyte peristaltic pump and a water bath cooling device, which can prevent the temperature of the catholyte from rising continuously due to electricity and heat generation. high to keep the reaction temperature constant. The cooling unit can cooperate with the heating unit to expand the precision and range of temperature regulation.

3) In addition, the present invention can also utilize a sampling unit, in particular, a sampling port can be set at infinitely close to the surface of the catalytic electrode to realize on-line sampling of the catholyte, and the in-situ detection of the catholyte reaction can be realized by being transported to an analytical instrument by a peristaltic pump. , so as to accurately monitor the progress of the reaction and the degree of hydrogenation. The sampling unit in the present invention can be composed of a capillary sampling tube and a peristaltic pump. The sampling port is close to the surface of the catalytic electrode to realize on-line sampling of the catholyte, which is transported and collected by the peristaltic pump and sent to the analysis instrument to realize the in-situ detection of the catholyte reaction. .

4) The anodic/cathode chamber of the present invention has a labyrinth turbulence structure at the bottom, which can make the anolyte/catholyte generate partial backflow in the reaction chamber, improve the uniformity of the liquid in the chamber, and prolong the reaction time of the liquid on the electrode surface. At the same time, the anolyte/catholyte adopts the method of bottom in and top out, which is also to ensure the uniform flow of the liquid in the chamber.

【Description of drawings】

FIG. 1 is a trend diagram of the acetic acid content in the bio-oil after upgrading in Example 1 of the present invention (detected by gas chromatography-mass spectrometry GC-MS).

Fig. 2 is a trend diagram (detected by an ultraviolet fluorescence spectrometer) of the content of aromatic components in the bio-oil after upgrading in Example 1 of the present invention as a function of time.

Figure 3 is a comparison diagram of the molecular mass distribution changes of bio-oil before and after upgrading in Example 1 of the present invention (detected by Fourier transform ion cyclotron resonance mass spectrometer FT-ICR MS).

FIG. 4 is a system diagram of the device for electrochemical upgrading of bio-oil provided by the present invention.

Figure 5 is a schematic structural diagram of an electrolysis unit in the present invention.

FIG. 6 is a schematic diagram of the labyrinth-type turbulent flow structure at the bottom of the anode/cathode chamber in the present invention.

FIG. 7 is the hydrogenation yields of representative compounds of bio-oil in Example 8 of the present invention under different reaction temperature conditions.

The meanings of the reference numerals in Figure 5 are as follows: 1- Anode chamber, 2- Anode electrode, 3- Proton exchange membrane, 4- Catalytic electrode, 5- Conductive ring, 6- Cathode chamber, 7- Gasket, 8- Fastening bolts, 9-electrolyte inlet, 10-electrolyte outlet, 11-capillary sampling tube, 12-thermocouple jack, 13-resistance wire.

【detailed description】

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

The method for electrochemical upgrading of biological oil in the present invention may include the following steps:

(a) firstly adding a supporting electrolyte to the alcohol solvent, then mixing the bio-oil with the alcohol solvent, and using the mixed liquid as the catholyte for standby use; the addition of the supporting electrolyte can improve the conductivity of the bio-oil;

(b) Prepare an acid solution with a concentration of 0.2mol/L-1.0mol/L as the anolyte for standby use (the acid solution is a protic solvent, which can dissociate proton hydrogen in the solution, and the proton hydrogen passes through the cation exchange membrane and enters the catholyte Adsorbed on the cathode surface to provide hydrogen source for bio-oil hydrogenation);

(c) Assembly of the electrochemical reactor: prepare an H-type electrolytic cell, which is separated by a cation-exchange membrane in the middle, and the catholyte and anolyte are loaded into the two sides of the H-type electrolytic cell, respectively, and the working electrode is inserted into the catholyte. A platinum sheet electrode is inserted into the anolyte, and the electrode is connected with a galvanostat;

(d) After nitrogen or inert gas is introduced into the catholyte side, the power supply is turned on, and the reaction is carried out for 2-8 hours under the condition of 50-200 mA current to realize electrochemical upgrading of bio-oil.

In addition, in 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 in a mass ratio of 9:1-4:1, thereby improving the conductivity of the catholyte rate, reduce catholyte viscosity, and improve bio-oil upgrading efficiency.

The H-type electrolytic cell can be a single-membrane electrolytic cell or a double-membrane electrolytic cell. When a single-membrane electrolytic cell is used, the catholyte and anolyte are placed on both sides of the H-type electrolytic cell respectively, and the middle is separated by a cation-exchange membrane; A cation exchange membrane is used on the anolyte side. Both the cation exchange membrane and the anion exchange membrane can directly use known functional materials in the prior art. The exchange membrane allows the passage of proton hydrogen in the anolyte into the catholyte while effectively separating the anolyte from the catholyte).

The following are specific examples:

Example 1

This embodiment specifically includes the following steps:

(a) First, add 0.1 mol/L LiCl supporting electrolyte to methanol, then mix bio-oil and methanol at a mass ratio of 4:1, and the mixed liquid is used as catholyte for standby use;

(b) The dilute sulfuric acid solution with a concentration of 0.5 mol/L is configured as the anolyte for standby use;

(c) Assembly of the electrochemical reactor: prepare an H-type electrolytic cell, separated by a Nafion-117 cation exchange membrane in the middle, put the catholyte and anolyte on both sides of the H-type electrolytic cell, and insert platinum into the catholyte Sheet electrode, insert platinum sheet electrode in the anolyte, and connect the electrode with a galvanostat;

(d) After nitrogen gas was introduced into the catholyte side for 15min, the power was turned on, the constant current was 50mA, the reaction temperature was 20°C, and the reaction time was 8h, so as to realize the upgrading of bio-oil. The changes of acetic acid content in bio-oil with time, the changes of aromatic component content with time, and the changes of molecular weight before and after upgrading are shown in Figure 1, Figure 2 and Figure 3, respectively, during the upgrading process.

Figure 1 shows the trend of acetic acid content over time during the electrochemical upgrading reaction of bio-oil (sampling interval 2h). With the progress of the reaction, the acetic acid content gradually decreased, and the acetic acid content decreased by 54.5% after 8h.

Figure 2 shows the trend of the content of aromatic components over time during the electrochemical upgrading reaction of bio-oil (sampling interval is 2 hours).

Figure 3 shows the molecular weight changes of bio-oil before and after 8 hours of upgrading. It can be seen that for each molecular mass distribution interval, its abundance decreases, indicating that the molecular weight of bio-oil after upgrading is reduced, and the heavy group content decreased.

Example 2

The concentration of the anolyte dilute sulfuric acid used in this example is 0.2 mol/L, and other conditions are the same as those in Example 1. After 8 hours of upgrading, the content of acetic acid in the bio-oil decreased by 26.7%, the content of aromatic components decreased by 34.1%, and the molecular weight of the bio-oil decreased.

Example 3

This embodiment specifically includes the following steps:

(a) firstly adding 0.1mol/L Bu ₄ NBF ₄ supporting electrolyte to methanol, then mixing bio-oil and methanol in a mass ratio of 6:1, and the mixed liquid is used as catholyte for use;

(b) The dilute sulfuric acid solution with a concentration of 0.5 mol/L is configured as the anolyte for standby use;

(c) Assembly of the electrochemical reactor: prepare an H-type electrolytic cell, the middle is separated by a Nafion-117 cation exchange membrane, the catholyte and the anolyte are loaded into the two sides of the H-type electrolytic cell, respectively, and carbon is inserted into the catholyte. For the ruthenium-based electrode, a platinum sheet electrode is inserted into the anolyte, and the electrodes are connected with a galvanostat; the carbon-based ruthenium electrode is prepared by electroplating (for the specific process of electroplating, please refer to the relevant prior art directly).

(d) After the nitrogen gas was introduced into the catholyte side for 15 minutes, the power was turned on, the constant current was 100 mA, the reaction temperature was 40 °C, and the reaction time was 2 h. The bio-oil was upgraded, and the acetic acid content of the bio-oil was reduced by 18.3% and the content of aromatic components by 46.0 %, the molecular weight of bio-oil decreases.

Example 4

This embodiment specifically includes the following steps:

(a) First, add 0.1 mol/L LiCl supporting electrolyte to methanol, then mix bio-oil and methanol at a mass ratio of 9:1, and the mixed liquid is used as catholyte for standby use;

(b) The dilute hydrochloric acid solution with a concentration of 0.5 mol/L is used as the anolyte for standby use;

(c) Assembly of the electrochemical reactor: Prepare an H-type electrolytic cell, separated by a Nafion-117 cation exchange membrane in the middle, put the catholyte and anolyte on both sides of the H-type electrolytic cell, respectively, insert Ni in the catholyte -Fe-modified nickel foam electrode, a platinum sheet electrode is inserted into the anolyte, and the electrode is connected with a galvanostat; Ni-Fe-modified nickel foam electrode is prepared by dipping method (for the specific process of the dipping method, you can directly refer to the relevant prior art ).

(d) After the nitrogen gas was introduced into the catholyte side for 15 minutes, the power was turned on, the constant current was 200 mA, the reaction temperature was 60 °C, and the reaction time was 2 h to achieve the upgrading of bio-oil, the acetic acid content of the bio-oil was reduced by 37.5%, and the content of aromatic components was reduced by 65.7 %, the molecular weight of bio-oil decreases.

Example 5

This embodiment specifically includes the following steps:

(a) First, add 0.1 mol/L LiCl supporting electrolyte to methanol, then mix bio-oil and methanol at a mass ratio of 9:1, and the mixed liquid is used as catholyte for standby use;

(b) The dilute hydrochloric acid solution with a concentration of 0.5 mol/L is used as the anolyte for standby use;

(c) Assembly of the electrochemical reactor: prepare a double-membrane three-chamber electrolytic cell, Nafion-117 cation exchange membrane on one side of the anolyte, an anion exchange membrane for the catholyte, deionized water in the middle chamber, and the catholyte and anolyte They were installed on both sides of the H-type electrolytic cell, and nickel electrodes were inserted into the catholyte, and platinum sheet electrodes were inserted into the anolyte, and the electrodes were connected with a galvanostat.

(d) After the nitrogen gas was introduced into the catholyte side for 15 minutes, the power was turned on, the constant current was 200 mA, the reaction temperature was 40 °C, and the reaction time was 6 h to achieve the upgrading of the bio-oil, the acetic acid content of the bio-oil was reduced by 43.2%, and the content of aromatic components was reduced by 66.3 %, the molecular weight of bio-oil decreases. The acidic substances in the bio-oil are separated into the intermediate chamber.

Example 6

This embodiment specifically includes the following steps:

(a) First, add 0.2mol/L LiCl supporting electrolyte to methanol, then mix bio-oil and methanol in a mass ratio of 4:1, and the mixed liquid is used as catholyte for standby use;

(b) The dilute sulfuric acid solution with a concentration of 1.0 mol/L is configured as an anolyte for standby use;

(c) Assembly of the electrochemical reactor: prepare an H-type electrolytic cell, separated by a Nafion-117 cation exchange membrane in the middle, put the catholyte and anolyte on both sides of the H-type electrolytic cell, and insert platinum into the catholyte Sheet electrode, insert platinum sheet electrode in the anolyte, and connect the electrode with a galvanostat;

(d) After the nitrogen gas was introduced into the catholyte side for 15 minutes, the power was turned on, the constant current was 50 mA, the reaction temperature was 20 °C, and the reaction time was 8 h. The bio-oil was upgraded, and the acetic acid content of the bio-oil was reduced by 71.7% and the content of aromatic components by 63.4%. %, the molecular weight of bio-oil decreases.

The bio-oil used in the above-mentioned embodiment, for example, can be obtained directly through condensation after the agricultural and forestry waste biomass such as rice husk, straw, edible fungus substrate, tree branches or bark is pyrolyzed at a high temperature of 500 ° C (of course, the thermal The solution temperature can also adopt a high temperature higher than 500°C).

The ambient temperature of the above-mentioned embodiment is 20～60 ℃ (of course, the temperature can also be other temperatures, as long as the influence of the temperature on the reaction system still makes the reaction system meet the solution system required by the electrochemical reaction), the air pressure is normal. pressure.

Example 7

As shown in FIG. 4 , an embodiment of the present invention proposes a device for electrochemical hydrotreating bio-oil, the device including an electrolysis unit, a circulation unit, a heating unit, a cooling unit and a sampling unit.

The electrolysis unit includes an anode compartment, an anode electrode, a proton exchange membrane, a catalytic electrode, a conductive ring, and a cathode compartment. The anode chamber and the cathode chamber are solid PTFE blocks with square grooves, the grooves are the anolyte/catholyte flow-through chambers, the anolyte/catholyte inlet is located at the bottom of the groove, and the outlet is located at the top of the side of the groove , the inlet and outlet of the anode chamber and the cathode chamber are located on both sides of the chamber, so that the inlet and outlet interfaces of the cathode and anode chambers do not interfere when connecting external pipes. The bottom of the chamber can be provided with a labyrinth turbulence structure (as shown in Figure 6), which can make the anolyte/catholyte generate local backflow in the reaction chamber, improve the uniformity of the liquid in the chamber, and prolong the reaction time of the liquid on the electrode surface .

The anode electrode is a mesh metal electrode, such as a platinum mesh electrode and a copper mesh electrode. The mesh electrode is used to ensure sufficient contact between the anolyte and the proton exchange membrane while conducting electricity, so that the adsorbed hydrogen can be transported to the cathode chamber through the exchange membrane. In this example, platinum mesh was used as the anode electrode.

The catalytic electrode is a catalyst modified electrode based on activated carbon cloth or carbon paper. In this example, the ruthenium catalyst is supported on the activated carbon cloth. First, soak a piece of activated carbon cloth in Ru(NH ₃ ) ₆ Cl ₃ solution to saturate the pores of the activated carbon cloth. After the pores of the activated carbon cloth are saturated with the solution, use a dust-free paper to absorb the excess solution. The activated carbon cloth was then dried by natural evaporation and then vacuum at room temperature. Finally, the impregnated activated carbon cloth was reduced with H in a reaction kettle at 3.0 MPa and ₂₀₀ °C to obtain the catalytic electrode used in this example.

The type of proton exchange membrane in this example is Nafion-117.

The conductive ring in this embodiment is a platinum sheet conductive ring (the conductive ring can also be other metal materials such as copper, which can play the role of connecting the catalytic electrode with the negative electrode of the power supply).

The anode electrode is close to the proton exchange membrane and is connected to the positive electrode of the DC power supply. The catalytic electrode is located between the proton exchange membrane and the conductive ring, and is connected to the negative electrode of the DC power supply through the conductive ring. A circle of polytetrafluoroethylene gaskets is arranged between the anode electrode and the anode chamber and between the conductive ring and the cathode chamber. The above components are connected in sequence and fixed and assembled and sealed by bolts and sealing gaskets, and finally constitute an electrolysis unit.

Connect the peristaltic pump and the bio-oil/anolyte storage tank to the inlet and outlet of the anode/cathode chamber through connecting pipes to form a circulation unit (as shown in Figure 4). The bio-oil sample and anolyte were injected into the bio-oil storage tank and the anolyte storage tank, respectively. The bio-oil used in this example was obtained by pyrolysis of rice husks at 500°C, dissolved and diluted with methanol and dichloromethane, and used as a bio-oil sample. The anolyte used in this embodiment is a 1 mol/L dilute sulfuric acid solution.

The peristaltic pump was turned on, and nitrogen gas was introduced into the bio-oil storage tank to remove the air in the cathode chamber and its circulation pipeline. At the same time, place the cooling coil in a constant temperature water bath cooling container. After 15min, turn on the DC power supply, circulate in the system through a peristaltic pump with a flow rate of 40mL/min, and keep the reaction temperature at 40°C in a constant temperature water bath to achieve isothermal reaction conditions. Use constant current mode to start the quality improvement test. Bio-oil samples were reacted with a constant current of 60 mA for 6 hours in the voltage range of 2.5-3.0 V. The product was analyzed by gas chromatography-mass spectrometer, and it was found that the content of ketones, phenols and furans in the bio-oil decreased, while the content of alcohols increased. It can be seen that the unsaturated components in the bio-oil are converted into corresponding saturated components through hydrogenation. The hydrogenation products and yields of representative compounds are shown in Table 1.

serial number	initial compound	Hydrogenation product		Yield%
1	Hydroxyacetone	Propylene Glycol	88.3
2	cyclopentenone	Cyclopentanol	79.4
3	phenol	cyclohexanol	89.9
4	furfural	furfuryl alcohol	88.8

In the above-mentioned Embodiment 7, the sampling unit is an optional structure (that is, when the sampling function does not need to be used, the sampling unit may not be provided).

In addition, if the heating unit is turned on, the cooling unit needs to be turned on for use. If the heating unit is not activated, the temperature of the bio-oil increases as the reaction proceeds, and the cooling unit can be activated in time to maintain a constant temperature as needed.

Example 8

Different from Example 7, in this example, a heating unit is used to control the reaction temperature. The heating unit is composed of a cathode chamber heating resistance wire, a thermocouple, a thermostat and a DC power supply. The resistance wire is laid on the back of the cathode chamber (that is, the resistance wire is arranged on the back of the groove). The top of the cathode chamber is provided with a capillary sampling tube and a thermocouple jack, and the thermocouple is inserted into the jack reserved for the cathode chamber. By controlling the reaction temperature in the cathode chamber, the bio-oil samples were subjected to constant current hydrogenation upgrading under the temperature conditions of 30°C, 40°C, 50°C, 60°C, and 70°C, respectively. The hydrogenation yields of bio-oil representative compounds at different reaction temperatures are shown in Figure 7.

Example 9

Different from Example 7, in this example, a sampling unit is used to realize on-line monitoring of the bio-oil sample hydro-upgrading process. The sampling unit consists of a capillary sampling tube and a peristaltic pump. The sampling port is close to the surface of the catalytic electrode to realize on-line sampling of the catholyte, which is transported and collected by a peristaltic pump, and then sent to analytical instruments, such as gas chromatography mass spectrometer and ultraviolet fluorescence spectrometer, which can realize in-situ detection of reaction products. During operation, the timed sample collection is realized by adjusting the flow rate of the peristaltic pump. The collected samples are immediately diluted with methanol to a concentration suitable for the analysis instrument, and then sent to the ultraviolet fluorescence spectrum analyzer and the gas chromatography mass spectrometer for analysis. Through real-time monitoring, the degree of bio-oil hydro-upgrading can be assessed, and the process can be regulated by adjusting the potential or temperature or reaction time.

Example 10

Different from Example 7, the cathode catalyst was directly coated on the side of the proton exchange membrane close to the cathode chamber (the anode side was not coated) to form a catalyst-coated membrane. At the same time, the catalytic electrode is cancelled, and the conductive ring is directly attached to the exchange membrane to form a new cathode. The Ru(NH ₃ ) ₆ Cl ₃ solution was mixed with 5% Nafion solution and coated on the proton exchange membrane to form a square catalyst coating. The advantage of omitting the activated carbon cloth is that the resistance between the cathode conductive ring and the catalyst can be reduced, and the Faradaic efficiency of the reaction can be improved to a certain extent.

In the above Examples 7-10, the specific raw materials used in each component can also be replaced by materials with the same function known in the prior art, for example, other known proton exchange membranes in the prior art can be used for proton exchange membranes.

Those skilled in the art can easily understand that the above are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, etc., All should be included within the protection scope of the present invention.

Claims (20)

1. A method for electrochemical upgrading of biological oil, comprising the following steps:

   (a) mixing the bio-oil, the organic solvent and the supporting electrolyte, and the liquid obtained by mixing is used as the catholyte for standby use; wherein, the supporting electrolyte is used to improve the electrical conductivity;

   (b) preparing an acid solution with a concentration of 0.2-1.0 mol/L as the anolyte for standby use;

   (c) using the catholyte and the anolyte to form an electrochemical reactor, inserting a working electrode into the catholyte, inserting an anode electrode into the anolyte, and passing between the catholyte and the anolyte 1 or 2 ion exchange membranes are separated and can form a current loop;

   (d) after the protective gas is introduced into the catholyte side, electric current is passed through the working electrode and the anode electrode to carry out an electrochemical reaction; the electrochemical reaction is a reaction under the condition of 50-200mA current 2-8h, thus the electrochemical upgrading of bio-oil can be realized.
2. The method for electrochemical upgrading of bio-oil according to claim 1, characterized in that, in the step (a), the bio-oil is obtained by pyrolysis of agricultural and forestry waste biomass at a high temperature of not less than 500° C. directly obtained by condensation;

   Preferably, the agricultural and forestry waste biomass is rice husk, straw, edible fungus substrate, tree branches or bark.
3. The method for electrochemical upgrading of bio-oil according to claim 1, characterized in that, in the step (a), the organic solvent is an alcohol solvent, preferably one of methanol, ethanol, n-propanol or isopropanol. one or more; the mass ratio of the biological oil component and the alcohol solvent component in the catholyte satisfies 9:1-4:1.
4. The method for electrochemical upgrading of bio-oil according to claim 1, wherein in the step (a), the supporting electrolyte is lithium chloride (LiCl), tetrabutyl hexafluorophosphate (Bu ₄ NPF ₆ ) ) or tetrabutyltetrafluoroborate (Bu ₄ NBF ₄ ), the concentration of the supporting electrolyte in the catholyte is 0.1-0.2 mol/L.
5. The method for electrochemical upgrading of bio-oil according to claim 1, wherein in the step (b), the acid is sulfuric acid, hydrochloric acid, perchloric acid or phosphoric acid.
6. The method for electrochemical upgrading of bio-oil according to claim 1, characterized in that, in the step (c), the electrochemical reactor is based on an H-type electrolytic cell, and the catholyte and the anolyte are located in the The two sides of the H-type electrolytic cell are separated by a cation exchange membrane in the middle.
7. The method for electrochemical upgrading of bio-oil according to claim 1, wherein, in the step (c), the electrochemical reactor is based on a single-membrane two-chamber electrolysis cell or a double-membrane three-chamber electrolysis cell;

   When based on a single-membrane double-chamber electrolysis cell, the catholyte and the anolyte are located on both sides of the single-membrane double-chamber electrolysis cell, and the middle is separated by a cation exchange membrane;

   When based on a double-membrane three-chamber electrolysis cell, the catholyte and the anolyte are located on both sides of the double-membrane three-chamber electrolysis cell, respectively, and are connected through an intermediate chamber; the catholyte is separated from the intermediate chamber by an anion exchange membrane, The anolyte is separated from the intermediate chamber by a cation exchange membrane.
8. The method for electrochemical upgrading of bio-oil 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 nickel electrodes, ruthenium electrodes, palladium electrodes, platinum electrodes, copper electrodes, gold electrodes, and stainless steel electrodes; the metal material modified electrodes It is obtained by processing a base material with a metal material. The base material is selected from carbon fiber cloth, activated carbon cloth, glass carbon fiber paper, carbon paper, graphite sheet, and nickel foam. The metal material is iron, nickel, ruthenium, palladium, or platinum. The salt of the element is preferably 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 method for electrochemical upgrading of bio-oil according to claim 8, wherein the metal material modified electrode is obtained by dipping, electroplating or hydrothermal treatment.
10. The method for electrochemical upgrading of bio-oil according to claim 1, wherein in the step (d), the protective gas is nitrogen or an inert gas; preferably, the inert gas is argon or helium .
11. A bio-oil electrochemical hydrogenation and upgrading device is characterized in that, comprising an electrolysis unit, a circulation unit and a heating unit, wherein,

    The electrolysis unit comprises an anode chamber (1) and a cathode chamber (6), the anode chamber (1) and the cathode chamber (6) are located in a relatively sealed space composed of acid-resistant materials, and both pass through a proton exchange membrane (3) Interphase; wherein, the anode chamber (1) is used for accommodating anolyte, and the cathode chamber (6) is used for accommodating bio-oil; the electrolysis unit can pass the anode electrode (2) and the cathode electrode to all The anode chamber (1) and the cathode chamber (6) provide direct current, so that the bio-oil in the cathode chamber (6) is electrochemically hydrotreated, so as to realize the upgrading of the bio-oil;

    The lower part of the anode chamber (1) and the cathode chamber (6) are provided with an electrolyte inlet (9), and the upper part is provided with an electrolyte outlet (10); the circulation unit is located outside the electrolysis unit, It includes a bio-oil circulation unit and an anolyte circulation unit; wherein, the electrolyte inlet (9) of the cathode chamber (6) is connected with the electrolyte outlet (10) through the bio-oil circulation unit, and a closed circulation loop can be formed; the The electrolyte inlet (9) of the anode chamber (1) is connected with the electrolyte outlet (10) through the anolyte circulation unit, which can form a circulation loop;

    The heating unit is used for heating the bio-oil in the cathode chamber (6), so that the bio-oil can be electrochemically hydrotreated under a preset temperature condition.
12. The device for electrochemical hydrogenation and upgrading of bio-oil according to claim 11, wherein the heating unit is composed of a cathode chamber heating resistance wire, a thermocouple, a temperature controller and a DC power supply, wherein the cathode chamber heating resistance The wire is laid on the back of the cathode chamber (6) for connecting with the DC power supply, and the joint for connecting with the DC power supply is reserved outside the cathode chamber (6); the thermocouple Used to detect the temperature of the biological oil in the cathode chamber (6), the thermostat is used to control the output power of the DC power supply according to the temperature detected by the thermocouple to change the heating resistance wire of the cathode chamber The power achieves the purpose of controlling the temperature of the electrolyte in the cathode compartment.
13. The device for electrochemical hydrogenation and upgrading of bio-oil according to claim 11, characterized in that the electrochemical hydrotreating is carried out under catalyst conditions, the cathode electrode is a conductive ring (5), and the conductive ring (5) connecting with the proton exchange membrane (3) through a catalytic electrode (4); preferably, the catalytic electrode (4) is an electrode based on activated carbon cloth or carbon paper and modified by the catalyst, The catalyst is a salt of Ru, Pt, Pd, Ni, or Fe element, preferably Ru(NH ₃ ) ₆ Cl ₃ , H ₂ PtCl ₆ , Pd(NO ₃ ) ₂ , Ni(NO ₃ ) ₂ or Fe( NO ₃ ) ₃ ;

    The anode electrode is a mesh metal electrode.
14. The device for electrochemical hydrogenation and upgrading of bio-oil according to claim 11, characterized in that the electrochemical hydrotreating is carried out under catalyst conditions, the cathode electrode is a conductive ring (5), and the conductive ring (5) directly connected to the proton exchange membrane (3), the catalyst coating membrane is also coated on the side of the proton exchange membrane (3) close to the cathode chamber (6), and the catalyst is Ru, Pt , Pd, Ni, or Fe element salt, preferably Ru(NH ₃ ) ₆ Cl ₃ , H ₂ PtCl ₆ , Pd(NO ₃ ) ₂ , Ni(NO ₃ ) ₂ or Fe(NO ₃ ) ₃ ;

    The anode electrode is a mesh metal electrode.
15. The bio-oil electrochemical hydro-upgrading device according to claim 11, wherein the bio-oil circulation unit comprises a peristaltic pump and a bio-oil storage tank located on the pipeline, and the anolyte circulation unit comprises a bio-oil circulation unit located on the pipeline peristaltic pump and anolyte storage tank;

    The bio-oil circulation unit is also connected with a cooling unit, and the cooling unit is capable of cooling the bio-oil in the bio-oil circulation unit.
16. The bio-oil electrochemical hydro-upgrading device according to claim 11, characterized in that, the bio-oil electrochemical hydro-upgrading device further comprises a sampling unit, and the sampling unit comprises a capillary sampling tube (11) and a peristaltic pump , the capillary sampling tube (11) is connected with the inside of the cathode chamber (6), and is used for sampling the biological oil in the cathode chamber (6) under the action of a peristaltic pump.
17. The device for electrochemical hydrogenation and upgrading of bio-oil according to claim 16, wherein the sampling unit is further connected with an ultraviolet fluorescence spectrometer and a gas chromatography mass spectrometer, the ultraviolet fluorescence spectrometer and the gas chromatograph A mass spectrometer is used to analyze the bio-oil sampled by the sampling unit.
18. The device for electrochemical hydrogenation and upgrading of bio-oil according to claim 11, characterized in that the acid-resistant material is polytetrafluoroethylene, and the anode chamber (1) and the cathode chamber (6) are respectively arranged in two blocks In the groove of the solid polytetrafluoroethylene block with grooves, a relatively sealed space is formed by splicing the two polytetrafluoroethylene blocks together with the sealing gasket (7); preferably, the sealing gasket (7) For the PTFE gasket.
19. The device for electrochemical hydrogenation and upgrading of bio-oil according to claim 11, wherein the electrolyte inlet (9) is located at the bottom of the anode chamber (1) and the cathode chamber (6), respectively, and the Electrolyte outlets (10) are located at the top sides of the anode chamber (1) and the cathode chamber (6), respectively.
20. The device for electrochemical hydrogenation and upgrading of bio-oil according to claim 11, characterized in that a labyrinth-type turbulence structure is provided at the bottom of both the anode chamber (1) and the cathode chamber (6).

Images