WO2022021909A1 - 一种生物油电化学提质方法及生物油电化学加氢提质装置 - Google Patents

一种生物油电化学提质方法及生物油电化学加氢提质装置 Download PDF

Info

Publication number
WO2022021909A1
WO2022021909A1 PCT/CN2021/083454 CN2021083454W WO2022021909A1 WO 2022021909 A1 WO2022021909 A1 WO 2022021909A1 CN 2021083454 W CN2021083454 W CN 2021083454W WO 2022021909 A1 WO2022021909 A1 WO 2022021909A1
Authority
WO
WIPO (PCT)
Prior art keywords
bio
oil
electrochemical
upgrading
electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/083454
Other languages
English (en)
French (fr)
Inventor
汪一
邓伟
熊哲
汪雪棚
邓增通
陈元静
向军
胡松
苏胜
江龙
徐俊
韩亨达
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN202010745427.XA external-priority patent/CN111871350B/zh
Priority claimed from CN202010745400.0A external-priority patent/CN111909736B/zh
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Publication of WO2022021909A1 publication Critical patent/WO2022021909A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
    • C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only

Definitions

  • 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.
  • 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.
  • bio-oil must be refined to improve fuel properties or to refine high value-added chemicals.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a method for electrochemical upgrading of biological oil is provided, which is characterized in that, comprising the following steps:
  • 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;
  • the agricultural and forestry waste biomass is rice husk, straw, edible fungus substrate, tree branches or bark.
  • 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.
  • 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.
  • the acid is sulfuric acid, hydrochloric acid, perchloric acid or phosphoric acid.
  • 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.
  • the electrochemical reactor is based on a single-membrane two-chamber electrolysis cell or a double-membrane three-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;
  • 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.
  • 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 .
  • the metal material modified electrode is obtained by dipping, electroplating or hydrothermal treatment.
  • the protective gas is nitrogen or an inert gas; preferably, the inert gas is argon or helium.
  • a bio-oil electrochemical hydro-upgrading device 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.
  • 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.
  • the electrochemical hydroprocessing is carried out under catalyst conditions
  • the cathode electrode is a conductive ring (5)
  • 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.
  • the electrochemical hydroprocessing is carried out under catalyst conditions
  • the cathode electrode is a conductive ring (5)
  • 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)
  • 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.
  • the bio-oil circulation unit includes a peristaltic pump and a bio-oil storage tank located on the pipeline
  • 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.
  • 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.
  • 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.
  • 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.
  • the acid-resistant material is polytetrafluoroethylene
  • the anode chamber (1) and the cathode chamber (6) are respectively arranged in the grooves of two solid polytetrafluoroethylene blocks with grooves
  • 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.
  • 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).
  • a labyrinth turbulence structure is provided at the bottom of both the anode chamber (1) and the cathode chamber (6).
  • 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.
  • 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.
  • 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).
  • normal temperature such as 20 to 25° C., of course, other temperatures of 20 to 60° C.
  • 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
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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;
  • 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.
  • bio-oil electrochemical hydrogenation upgrading device in the present invention compared with the prior art, can also achieve the following beneficial effects:
  • 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.
  • the anode chamber is the circulation chamber of anolyte (protic solvent)
  • the cathode chamber is the circulation chamber of catholyte (bio-oil).
  • the present invention can use a catalytic electrode, for example, a catalyst-modified electrode based on activated carbon cloth or carbon paper.
  • a catalytic electrode for example, a catalyst-modified electrode based on activated carbon cloth or carbon paper.
  • 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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.
  • 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 method for electrochemical upgrading of biological oil in the present invention may include the following steps:
  • 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.
  • a single-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).
  • 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.
  • 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.
  • the dilute sulfuric acid solution with a concentration of 1.0 mol/L is configured as an anolyte for standby use;
  • the bio-oil used in the above-mentioned embodiment 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 °C (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.
  • 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 .
  • a labyrinth turbulence structure as shown in Figure 6
  • 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.
  • platinum mesh was used as the anode electrode.
  • the catalytic electrode is a catalyst modified electrode based on activated carbon cloth or carbon paper.
  • the ruthenium catalyst is supported on the activated carbon cloth.
  • 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 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 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).
  • 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.
  • 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.
  • 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.
  • analytical instruments such as gas chromatography mass spectrometer and ultraviolet fluorescence spectrometer, which can realize in-situ detection of reaction products.
  • 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.
  • 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.
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

本发明属于生物质能利用领域，公开了一种生物油电化学提质方法及生物油电化学加氢提质装置，其中生物油电化学提质方法包括以下步骤：(a)将生物油、有机溶剂和支持电解质混合得到阴极液；(b)准备酸溶液作为阳极液；(c)采用阴极液和阳极液组建电化学反应器，阴极液与阳极液之间通过1或2个离子交换膜相隔，并能够形成电流回路；(d)在阴极液一侧通入保护性气体后，通过工作电极和阳极电极通入电流以进行电化学反应，由此即可实现生物油电化学提质。本发明能够有效解决热化学方法提质生物油易形成积碳的问题，在温和条件下对生物油进行电化学提质，提质可降低生物油酸含量、芳香组分含量和重质组分含量，使得生物油适合于运输和储存。

Description

一种生物油电化学提质方法及生物油电化学加氢提质装置 【技术领域】
本发明属于生物质能利用领域，更具体地，涉及一种生物油电化学提质方法及生物油电化学加氢提质装置。
【背景技术】
生物油是生物质的热解产物，是唯一以液体形式存在的含碳可再生能源。与生物质相比，生物油能量密度高，通常可达生物质能量密度的10倍。将生物质转化为生物油是一种有前景的生物质能低成本利用方式。然而，生物油目前仍未有成熟的可工业化的应用或处理技术。导致生物油的难处理、难应用的根本原因是其特有的物理化学特性。生物油成分复杂、酸值高、粘度大、具有腐蚀性，导致其难以进行大规模的运输和储存。生物油含氧量高、重质组分多(分子量高)、热值低，导致难以直接应用于燃烧设备。因此，生物油必须经过精制提质以提高燃料性质或提炼高附加值化学品。目前对生物油的提质方法主要是基于热化学的加氢脱氧、催化裂解、水蒸气重整等传统方法，处理过程需要在高温或高气压环境下进行。然而，生物油热稳定性差，受热易结焦形成积碳，造成反应器堵塞或催化剂失活，降低提质效率，甚至导致反应难以进行。
鉴于上述情况，研发一种温和条件(如常温常压)下的生物油提质方法将具有重要应用价值。
与此同时，虽然利用生物质快速热解生产生物油、燃料气、生物炭等已成为生物质资源利用的有效途径，然而生物油由于其高粘度、高水分、高含氧量、腐蚀性和化学不稳定性等特性，直接应用受到限制。因此，在将生物油用于生产液体燃料之前应对其进行加氢提质。传统加氢提质过程均在高温下进行，然而，生物油受热易聚合，在高温下因其热不稳定性而聚合形成焦炭，堵塞催化剂活性位和反应器，影响提质过程的稳定性和寿命。鉴于上述情况，设计一种基于电化学的温和条件下的生物油加氢提质装置也非常必要。
【发明内容】
针对现有技术的以上缺陷或改进需求，本发明的目的在于提供一种生物油电化学提质方法及生物油电化学加氢提质装置，其中就生物油电化学提质方法而言，通过对提质方法所采用的电化学处理、以及电化学处理所采用的具体参数、条件等进行改进，与现有技术相比能够有效解决传统热化学方法提质生物油易形成积碳的问题，本发明能够在温和条件(如常温常压)下对生物油进行电化学提质，提质可降低生物油酸含量、芳香组分含量和重质组分含量，使得生物油适合于运输和储存，同时在提质过程中避免积碳的产生；而对生物油电化学加氢提质装置来说，通过对装置各组件的结构及它们的设置方式等进行改进，与现有技术相比，能够实现在恒定温度下的生物油电化学加氢提质，并可进一步通过阴极室的结构设计，同时实现电极表面生物油的在线取样。
为实现上述目的，按照本发明的一个方面，提供了一种生物油电化学提质方法，其特征在于，包括以下步骤：
(a)将生物油、有机溶剂和支持电解质三者混合，混合得到的液体作为阴极液备用；其中，所述支持电解质用以提高电导率；
(b)准备浓度为0.2-1.0mol/L的酸溶液作为阳极液备用；
(c)采用所述阴极液和所述阳极液组建电化学反应器，向所述阴极液中插入工作电极，所述阳极液中插入阳极电极，所述阴极液与所述阳极液之间通过1个或2个离子交换膜相隔，并能够形成电流回路；
(d)在所述阴极液一侧通入保护性气体后，通过所述工作电极和所述阳极电极通入电流以进行电化学反应；所述电化学反应是在50-200mA电流条件下反应2-8h，由此即可实现生物油电化学提质。
作为本发明的进一步优选，所述步骤(a)中，所述生物油是由农林废弃物生物质在不低于500℃的高温下热解后经过冷凝直接得到的；
优选的，所述农林废弃物生物质为稻壳、秸秆、食用菌基质、林木枝桠或树皮。
作为本发明的进一步优选，所述步骤(a)中，所述有机溶剂为醇类溶剂，优选为甲醇、乙醇、正丙醇或异丙醇的一种或多种；所述阴极液中生物油组分与醇 类溶剂组分的质量比满足9:1-4:1。
作为本发明的进一步优选，所述步骤(a)中，所述支持电解质为氯化锂(LiCl)、四丁基六氟磷酸盐(Bu 4NPF 6)或四丁基四氟硼酸盐(Bu 4NBF 4)，所述支持电解质在所述阴极液中的浓度为0.1-0.2mol/L。
作为本发明的进一步优选，所述步骤(b)中，所述酸为硫酸、盐酸、高氯酸或磷酸。
作为本发明的进一步优选，所述步骤(c)中，所述电化学反应器是基于H型电解池，所述阴极液和所述阳极液分别位于该H型电解池的两侧，中间通过阳离子交换膜隔开。
作为本发明的进一步优选，所述步骤(c)中，所述电化学反应器是基于单膜双室电解池或双膜三室电解池；
当基于单膜双室电解池时，所述阴极液和所述阳极液分别位于该单膜双室电解池的两侧，中间由阳离子交换膜相隔；
当基于双膜三室电解池时，所述阴极液和所述阳极液分别位于该双膜三室电解池的两侧，通过中间室相连；所述阴极液通过阴离子交换膜与所述中间室相隔，所述阳极液通过阳离子交换膜与所述中间室相隔。
作为本发明的进一步优选，所述步骤(c)中，所述阳极电极为铂电极、钌电极、钯电极、或镍电极；
所述工作电极为金属材料电极或金属材料修饰电极；其中，所述金属材料电极选自镍电极、钌电极、钯电极、铂电极、铜电极、金电极、不锈钢电极；所述金属材料修饰电极是利用金属材料处理基底材料得到的，所述基底材料选自碳纤维布、活性炭布、玻璃碳纤维纸、碳纸、石墨片、泡沫镍，所述金属材料为铁、镍、钌、钯、或铂元素的盐，优选为Fe(NO 3) 3、Ni(NO 3) 2、Ru(NH 3) 6Cl 3、Pd(NO 3) 2或H 2PtCl 6。
作为本发明的进一步优选，所述金属材料修饰电极是通过浸渍法、电镀法或水热法处理得到的。
作为本发明的进一步优选，所述步骤(d)中，所述保护性气体为氮气或惰性 气体；优选的，所述惰性气体为氩气或氦气。
按照本发明的另一方面，提供了一种生物油电化学加氢提质装置，其特征在于，包括电解单元、循环单元和加热单元，其中，
所述电解单元包括阳极室(1)和阴极室(6)，所述阳极室(1)和所述阴极室(6)位于由耐酸材料构成的相对密封的空间内，两者通过质子交换膜(3)相间隔；其中，所述阳极室(1)用于容纳阳极液，所述阴极室(6)用于容纳生物油；所述电解单元能够通过阳极电极(2)和阴极电极向所述阳极室(1)和所述阴极室(6)提供直流电，使所述阴极室(6)内的生物油进行电化学加氢处理，实现对生物油的提质；
所述阳极室(1)和所述阴极室(6)的下部均开设有电解液进口(9)，上部均开设有电解液出口(10)；所述循环单元位于所述电解单元的外部，包括生物油循环单元和阳极液循环单元；其中，所述阴极室(6)的电解液进口(9)与电解液出口(10)通过生物油循环单元相连，能够形成封闭的循环回路；所述阳极室(1)的电解液进口(9)与电解液出口(10)通过阳极液循环单元相连，能够形成循环回路；
所述加热单元用于对所述阴极室(6)内的生物油进行加热，使这些生物油能够在预先设定的温度条件下进行电化学加氢处理。
作为本发明的进一步优选，所述加热单元由阴极室加热电阻丝、热电偶、温控器和直流电源组成，其中，所述阴极室加热电阻丝敷设于所述阴极室(6)的背面，用于与所述直流电源相连，并且，用于与该直流电源连接的接头预留在所述阴极室(6)的外部；所述热电偶用于对所述阴极室(6)内的生物油的温度进行检测，所述温控器用于根据所述热电偶检测得到的温度控制所述直流电源输出功率来改变所述阴极室加热电阻丝功率达到控制所述阴极室电解液温度的目的。
作为本发明的进一步优选，所述电化学加氢处理是在催化剂条件下进行的，所述阴极电极为导电环(5)，所述导电环(5)通过催化电极(4)与所述质子交换膜(3)相连；优选的，所述催化电极(4)为以活性炭布或碳纸为基底的、且经所述催化剂修饰的电极，所述催化剂为Ru、Pt、Pd、Ni、或Fe元素的盐，优 选为Ru(NH 3) 6Cl 3、H 2PtCl 6、Pd(NO 3) 2、Ni(NO 3) 2或Fe(NO 3) 3；
所述阳极电极为网状金属电极。
作为本发明的进一步优选，所述电化学加氢处理是在催化剂条件下进行的，所述阴极电极为导电环(5)，所述导电环(5)直接与所述质子交换膜(3)相连，所述质子交换膜(3)靠近阴极室(6)的一面上还涂覆有所述催化剂涂层膜，所述催化剂为Ru、Pt、Pd、Ni、或Fe元素的盐，优选为Ru(NH 3) 6Cl 3、H 2PtCl 6、Pd(NO 3) 2、Ni(NO 3) 2或Fe(NO 3) 3；
所述阳极电极为网状金属电极。
作为本发明的进一步优选，所述生物油循环单元包括位于管道上的蠕动泵和生物油储罐，所述阳极液循环单元包括位于管道上的蠕动泵和阳极液储罐；
所述生物油循环单元还与冷却单元相连，所述冷却单元能够对所述生物油循环单元内的生物油进行冷却处理。
作为本发明的进一步优选，所述生物油电化学加氢提质装置还包括取样单元，所述取样单元包括毛细取样管(11)和蠕动泵，该毛细取样管(11)与所述阴极室(6)内部相连，用于在蠕动泵作用下对所述阴极室(6)内的生物油进行取样。
作为本发明的进一步优选，所述取样单元还与紫外荧光光谱分析仪和气相色谱质谱仪相连，所述紫外荧光光谱分析仪和所述气相色谱质谱仪用于对所述取样单元取样得到的生物油进行分析。
作为本发明的进一步优选，所述耐酸材料为聚四氟乙烯，所述阳极室(1)和所述阴极室(6)分别设置在2块带凹槽的实心聚四氟乙烯块的凹槽内，通过这2块聚四氟乙烯块的拼接配合密封垫片(7)形成相对密封的空间；优选的，所述密封垫片(7)为聚四氟乙烯密封垫片。
作为本发明的进一步优选，所述电解液进口(9)分别位于所述阳极室(1)和所述阴极室(6)的底部，所述电解液出口(10)分别位于所述阳极室(1)和所述阴极室(6)的侧面顶端。
作为本发明的进一步优选，在所述阳极室(1)和所述阴极室(6)的底部均设置有迷宫式扰流结构。
通过本发明所构思的生物油电化学提质方法，与现有技术相比，能够取得以下有益效果：
(1)本发明方法与现有生物油提质技术相比，最大的优势在于本发明针对的对象是生物油全组分，不需要预先将生物油进行分离，流程简单，同时最大程度保持了生物油中的碳质组分，便于提质后的进一步加工利用。
(2)本发明通过在电能作用下，生物油组分分子内C-O化学键的断裂、苯环加氢以及酸醇酯化反应的原位耦合，实现了温和条件下初步提质生物油的目的，使得生物油酸含量降低、芳香组分含量降低、重质组分含量降低，以便其更加适于运输和储存。本发明采用有机溶剂能够有效溶解生物油样品，降低其粘度，以便使生物油样品适于电解池中；同时，本发明优选采用醇类溶剂作为有机溶剂，这是因为醇类是生物油的主要组分之一，加入生物油后降低其粘度，但不会对其组分造成过多影响，便于生物油提质后直接利用。
(3)本发明反应条件温和，整个电化学处理过程是在常温(如20～25℃，当然也可以是在20～60℃的其他温度下)、常压(即，一个标准大气压)下进行的，工艺操作简单，反应过程无结焦积碳，反应启停迅速、可精准控制反应条件，可实现间断或连续反应。本发明方法优先在20～60℃条件下进行，以适合于生物油电化学提质，从而能够避免温度低于20℃时生物油中组分的反应性较低、提质效率低，以及温度高于60℃时析氢等副反应开始活跃、降低了提质效率等负面影响(当然，过高的温度也会导致醇类组分或溶剂蒸发，导致生物油流动性变差，影响反应进程)。
生物油具有粘度大、导电率低、对支持电解质溶解度低的特点，导致不适用于电化学方法处理。本发明采用有机溶剂(尤其是醇类溶剂)，一方面能够有效溶解生物油样品，降低其粘度，以便使生物油样品适于电解池中。另一方面，配合使用在这些有机溶剂中有较高溶解度的支持电解质，以优选使支持电解质在阴极液中的浓度达到0.1-0.2mol/L，可以克服支持电解质在生物油中溶解度低、生物油导电率低的缺点，提高生物油导电率。此外，本发明优选采用醇类溶剂作为有机溶剂，醇类溶剂的种类尤其可根据生物油中所含醇类组分确定，选择添加生物 油中本身含有的醇类溶剂，可以最大程度上减少对生物油本身组分的影响，便于提质后生物油进一步利用。以有机溶剂为醇类溶剂为例，本发明中的生物油与醇类溶剂比例优选为9:1-4:1，非常适合于生物油电化学提质，能够避免生物油/醇类溶剂比过低时，醇类溶剂过多，醇类溶剂挥发导致生物油中有机组分流失，影响提质效果；以及生物油/醇类溶剂比过高时，生物油流动性不足，不利于电化学提质，同时，过高的生物油浓度，导致电极表面吸附态反应物质位点饱和，反应效率低等负面影响。
生物油中的芳香族组分在电化学处理过程中容易在阳极发生氧化反应而聚合，在电极表面产生积碳。本发明采用离子交换膜的形式，确保生物油只在阴极一侧参与反应。一方面可以避免生物油在阳极聚合积碳，另一方面可有效去除生物油中的酸，降低生物油腐蚀性。采用三室双膜的形式，还可以将生物油中的酸分离，经过收集后，酸可作为本方法的副产品。
本发明中的电流范围50-200mA，是适合于生物油电化学提质的电流区间。电流与反应速率直接相关，进而影响提质效率。电流低于50mA，电极表面参与反应的电子、质子以及吸附态反应物数量不足，生物油提质效率不高；电流高于200mA，电极表面吸附态反应物质位点饱和，电流继续增加也不会带来提质反应强度的增加，反而导致析氢等副反应强度增加，降低了生物油提质效率，因此，本发明采用在50-200mA电流条件下进行电化学反应。
而本发明中的生物油电化学加氢提质装置，与现有技术相比，亦能够取得以下有益效果：
1)本发明提供的利用电化学进行生物油加氢提质的装置结构简单并且易于操作，仅需将生物油和质子性溶剂分别从液体储罐注入循环单元，开启蠕动泵并接通阳极电极和阴极电极(阴极电极尤其可以是催化电极)，便可实现对生物油的加氢提质。本发明中利用电化学加氢提质生物油的装置，其中的阳极室是阳极液(质子性溶剂)的流通腔室，阴极室是阴极液(生物油)的流通腔室，能够利用电化学方法加氢提质生物油。本发明尤其可采用催化电极，例如，以活性炭布或碳纸为基底的催化剂修饰电极，通过将催化剂负载于比表面积大、孔隙率高的碳 基基底上，增加催化剂与阴极液的接触面积和停留时间，从而提高反应效率。
2)同时，本发明在阴极室通流凹槽的背部植入电阻丝，能够对阴极液进行加热，实现在恒定温度下生物油电化学加氢。对于不同的生物油原料，可通过优化的温度参数提高加氢效率和目标产物选择性。也就是说，本发明通过设置加热单元，能够实现对阴极液的加热，使阴极液能够在最合适的温度范围内进行反应。另外，本发明尤其可设置冷却单元，配合加热单元共同使用；该冷却单元可以为阴极液蠕动泵进口前管道上的冷却盘管和水浴冷却装置组成，能够避免由于通电发热导致阴极液温度不断升高，从而保证反应温度恒定不变。该冷却单元可以和加热单元协同作用，扩大温度调控的精度和范围。
3)此外，本发明还可以利用取样单元，尤其可在无限接近催化电极表面处设置取样端口，实现对阴极液的在线取样，通过蠕动泵输送至分析仪器可实现对阴极液反应的原位检测，从而精确监测反应进程和加氢程度。本发明中的取样单元可由毛细取样管、蠕动泵组成，取样端口接近催化电极表面，实现对阴极液的在线取样，通过蠕动泵输送收集，送至分析仪器可实现对阴极液反应的原位检测。
4)本发明阳/阴极室腔室底部有迷宫式扰流结构，能够使得阳/阴极液在反应腔室内产生局部回流，改善液体在腔室内的均匀性，延长液体在电极表面的反应时间。同时，阳/阴极液均采用下进上出的方式，也是为了保证液体在腔室内的均匀流动。
【附图说明】
图1是本发明实施例1提质后的生物油中乙酸含量随时间变化趋势图(由气相色谱-质谱联用仪GC-MS检测)。
图2是本发明实施例1提质后的生物油中芳香组分含量随时间变化趋势图(由紫外荧光光谱仪检测)。
图3是本发明实施例1提质前后生物油分子质量分布变化对比图(由傅里叶变换离子回旋共振质谱仪FT-ICR MS检测)。
图4是本发明提供的生物油电化学提质装置的系统图。
图5是本发明中电解单元的结构示意图。
图6是本发明中阳/阴极室腔室底部迷宫式扰流结构示意图。
图7是本发明实施例8中生物油代表性化合物在不同反应温度条件下的加氢产率。
图5中各附图标记的含义如下：1－阳极室，2－阳极电极，3－质子交换膜，4－催化电极，5－导电环，6－阴极室，7－密封垫片，8－紧固螺栓，9－电解液进口，10－电解液出口，11－毛细取样管，12－热电偶插孔，13－电阻丝。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明中生物油电化学提质的方法，可以包括如下步骤：
(a)首先向醇类溶剂中加入支持电解质，再将生物油与醇类溶剂混合，混合液体作为阴极液备用；支持电解质的加入可以提高生物油的导电性；
(b)准备浓度为0.2mol/L-1.0mol/L的酸溶液作为阳极液备用(酸溶液为质子性溶剂，能在溶液中解离出质子氢，质子氢透过阳离子交换膜进入阴极液吸附于阴极表面，为生物油加氢提供氢源)；
(c)电化学反应器的组装：准备H型电解池，中间用阳离子交换膜隔开，将阴极液和阳极液分别装入H型电解池的两侧，在阴极液中插入工作电极，在阳极液中插入铂片电极，电极用恒电流仪连接；
(d)在阴极液一侧通入氮气或惰性气体后，打开电源，在50-200mA电流条件下，反应2-8h，实现生物油电化学提质。
另外，在步骤(a)中，支持电解质在阴极液中的浓度为0.1-0.2mol/L，生物油与醇类溶剂按9:1-4:1的质量比混合，从而提高阴极液的导电率，降低阴极液粘度，提高生物油提质效率。
H型电解池可以为单膜电解池或双膜电解池。当采用单膜电解池时，阴极液和阳极液分别装入H型电解池的两侧，中间用阳离子交换膜隔开；采用双膜三室 电解池时，在阴极液一侧采用阴离子交换膜，在阳极液一侧采用阳离子交换膜。阳离子交换膜、阴离子交换膜均可直接采用现有技术中的已知功能材料，例如，阳离子交换膜可以采用Nafion-1035、Nafion-115或Nafion-117膜等(以阳离子交换膜为例，阳离子交换膜允许阳极液中的质子氢通过进入阴极液，同时有效的将阳极液和阴极液隔离开)。
以下为具体实施例：
实施例1
本实施例具体包括以下步骤：
(a)首先向甲醇中加入0.1mol/L LiCl支持电解质，再将生物油与甲醇按4:1的质量比混合，混合液体作为阴极液备用；
(b)配置浓度为0.5mol/L的稀硫酸溶液作为阳极液备用；
(c)电化学反应器的组装：准备H型电解池，中间用Nafion-117阳离子交换膜隔开，将阴极液和阳极液分别装入H型电解池的两侧，在阴极液中插入铂片电极，在阳极液中插入铂片电极，电极用恒电流仪连接；
(d)在阴极液一侧通入氮气15min后，打开电源，定电流50mA，反应温度20℃，反应时间8h，实现生物油提质。提质过程中生物油中乙酸含量随时间的变化、芳香组分含量随时间的变化以及提质前后分子质量变化分别见图1、图2和图3。
图1是生物油电化学提质反应过程中乙酸含量随时间变化趋势图(取样间隔2h)，随着反应的进行，乙酸含量逐步降低，8h后乙酸含量降低54.5％。
图2是生物油电化学提质反应过程中芳香组分含量随时间变化趋势图(取样间隔2h)，随着反应的进行，芳香组分含量逐步降低，8h后芳香组分含量降低67.9％。
图3是生物油在提质前和经过8h提质后的分子质量变化，可见对于每段分子质量分布区间，其丰度均下降，说明经过提质后的生物油分子质量降低，重质组分含量降低。
实施例2
本实施例所采用的阳极液稀硫酸的浓度为0.2mol/L，其余条件与实施例1相同。经过8h提质后生物油乙酸含量降低26.7％，芳香组分含量降低34.1％，生物油分子质量降低。
实施例3
本实施例具体包括以下步骤：
(a)首先向甲醇中加入0.1mol/L Bu 4NBF 4支持电解质，再将生物油与甲醇按6:1的质量比混合，混合液体作为阴极液备用；
(b)配置浓度为0.5mol/L的稀硫酸溶液作为阳极液备用；
(c)电化学反应器的组装：准备H型电解池，中间用Nafion-117阳离子交换膜隔开，将阴极液和阳极液分别装入H型电解池的两侧，在阴极液中插入碳基钌电极，在阳极液中插入铂片电极，电极用恒电流仪连接；碳基钌电极采用电镀法制备(电镀法的具体过程，可直接参考相关现有技术)。
(d)在阴极液一侧通入氮气15min后，打开电源，定电流100mA，反应温度40℃，反应时间2h，实现生物油提质，生物油乙酸含量降低18.3％，芳香组分含量降低46.0％，生物油分子质量降低。
实施例4
本实施例具体包括以下步骤：
(a)首先向甲醇中加入0.1mol/L LiCl支持电解质，再将生物油与甲醇按9:1的质量比混合，混合液体作为阴极液备用；
(b)配置浓度为0.5mol/L的稀盐酸溶液作为阳极液备用；
(c)电化学反应器的组装：准备H型电解池，中间用Nafion-117阳离子交换膜隔开，将阴极液和阳极液分别装入H型电解池的两侧，在阴极液中插入Ni-Fe修饰的泡沫镍电极，在阳极液中插入铂片电极，电极用恒电流仪连接；Ni-Fe修饰的泡沫镍电极采用浸渍法制备(浸渍法的具体过程，可直接参考相关现有技术)。
(d)在阴极液一侧通入氮气15min后，打开电源，定电流200mA，反应温度60℃，反应时间2h，实现生物油提质，生物油乙酸含量降低37.5％，芳香组分含量降低65.7％，生物油分子质量降低。
实施例5
本实施例具体包括以下步骤：
(a)首先向甲醇中加入0.1mol/L LiCl支持电解质，再将生物油与甲醇按9:1的质量比混合，混合液体作为阴极液备用；
(b)配置浓度为0.5mol/L的稀盐酸溶液作为阳极液备用；
(c)电化学反应器的组装：准备双膜三室电解池，阳极液一侧Nafion-117阳离子交换膜，阴极液采用阴离子交换膜，中间腔室装入去离子水，将阴极液和阳极液分别装入H型电解池的两侧，在阴极液中插入镍电极，在阳极液中插入铂片电极，电极用恒电流仪连接。
(d)在阴极液一侧通入氮气15min后，打开电源，定电流200mA，反应温度40℃，反应时间6h，实现生物油提质，生物油乙酸含量降低43.2％，芳香组分含量降低66.3％，生物油分子质量降低。生物油中的酸性物质分离到中间腔室。
实施例6
本实施例具体包括以下步骤：
(a)首先向甲醇中加入0.2mol/L LiCl支持电解质，再将生物油与甲醇按4:1的质量比混合，混合液体作为阴极液备用；
(b)配置浓度为1.0mol/L的稀硫酸溶液作为阳极液备用；
(c)电化学反应器的组装：准备H型电解池，中间用Nafion-117阳离子交换膜隔开，将阴极液和阳极液分别装入H型电解池的两侧，在阴极液中插入铂片电极，在阳极液中插入铂片电极，电极用恒电流仪连接；
(d)在阴极液一侧通入氮气15min后，打开电源，定电流50mA，反应温度20℃，反应时间8h，实现生物油提质，生物油乙酸含量降低71.7％，芳香组分含量降低63.4％，生物油分子质量降低。
上述实施例中所采用的生物油，例如可以是稻壳、秸秆、食用菌基质、林木枝桠或树皮等农林废弃物生物质在500℃高温下热解后经过冷凝直接得到的(当然，热解温度也可以采用高于500℃的高温)。
上述实施例所处的环境温度为20～60℃(当然，温度也可以是其他温度，只 要温度对反应体系的影响仍然使反应体系满足电化学反应所要求的溶液体系即可)，气压为常压。
实施例7
如图4所示，本发明实施例提出了一种电化学加氢提质生物油的装置，该装置包括电解单元、循环单元、加热单元、冷却单元和取样单元。
电解单元包括阳极室、阳极电极、质子交换膜、催化电极、导电环、阴极室。其中，阳极室和阴极室为带有方形凹槽的实心聚四氟乙烯块，凹槽即为阳/阴极液通流腔室，阳/阴极液进口位于凹槽底部，出口位于凹槽侧面顶端，阳极室和阴极室的进出口分别位于腔室的两侧，以便连接外部管道时阴阳极腔室进出口接口不发生干涉。腔室底部可设有迷宫式扰流结构(如图6所示)，能够使得阳/阴极液在反应腔室内产生局部回流，改善液体在腔室内的均匀性，延长液体在电极表面的反应时间。
阳极电极为网状金属电极，如铂网电极、铜网电极。采用网状电极在导电的同时保证阳极液与质子交换膜充分接触，从而能够将吸附氢通过交换膜输送至阴极室。本实例中采用铂网作为阳极电极。
催化电极为以活性炭布或碳纸为基底的催化剂修饰电极。本实例中通过在活性炭布上负载钌催化剂。首先将一块活性炭布浸泡在Ru(NH 3) 6Cl 3溶液中，使活性炭布孔饱和。在活性炭布毛孔被溶液浸透后，用无尘纸吸除多余的溶液。然后在室温下先后通过自然蒸发和真空的方式对活性炭布进行干燥。最后，浸渍的活性炭布在3.0MPa和200℃的反应釜中用H 2还原，即可得到本实施例中所使用的催化电极。
本实施例中的质子交换膜型号为Nafion-117。
本实施例中的导电环为铂片导电环(导电环还可以是铜等其他金属材料，能够起到将催化电极与电源负极相连通的作用)。
阳极电极紧贴质子交换膜，并与直流电源正极相连。催化电极位于质子交换膜和导电环中间，并通过导电环与直流电源负极相连。阳极电极与阳极室之间、导电环与阴极室之间均设有一圈聚四氟乙烯垫片。上述组件依次连接并通过螺栓 和密封垫片实现固定和组装密封，最终组成电解单元。
将蠕动泵、生物油/阳极液储罐通过连接管道与阳/阴极室的进出口相连，组成循环单元(如图4所示)。分别向生物油储罐和阳极液储罐中注入生物油样品和阳极液。本实施例中所使用的生物油由稻壳在500℃条件下热解得到，通过甲醇和二氯甲烷进行溶解和稀释后作为生物油样品。本实施例中所使用的阳极液为1mol/L稀硫酸溶液。
开启蠕动泵，同时向生物油储罐中通入氮气，以便排除阴极室及其循环管路中的空气。同时将冷却盘管至于恒温水浴冷却容器中。15min后开启直流电源，通过流速为40mL/min的蠕动泵在系统中循环，恒温水浴使反应温度保持在40℃，达到等温反应条件。采用恒电流方式开始提质测试。生物油样品在2.5-3.0V的电压范围内，以60mA的恒定电流反应6小时。通过气相色谱质谱仪对产物进行分析发现生物油中酮类、酚类和呋喃类组分含量降低，而醇类组分含量升高。可见生物油中不饱和组分经过加氢转化为相应的饱和组分。其中代表性化合物加氢产物及产率如表1所示。
序号 初始化合物 加氢产物 产率％
1 羟基丙酮 丙二醇 88.3
2 环戊烯酮 环戊醇 79.4
3 苯酚 环己醇 89.9
4 糠醛 糠醇 88.8
上述实施例7中，取样单元为可选结构(也就是说，不需要使用取样功能时，可不设置取样单元)。
另外，若加热单元开启，则需要开启冷却单元配合使用。若加热单元不启用，随着反应进行，生物油温度升高，可以根据需要适时启动冷却单元维持温度恒定。
实施例8
区别于实施例7，本实施例中使用加热单元控制反应温度。加热单元由阴极室加热电阻丝、热电偶、温控器和直流电源组成。电阻丝敷设于阴极室背面(即，凹槽背面设置电阻丝)。阴极室顶部有毛细取样管和热电偶插孔，热电偶插入阴极室预留的插孔。通过控制阴极室反应温度，分别在30℃、40℃、50℃、60℃、 70℃温度条件下，进行恒定电流加氢提质生物油样品。生物油代表性化合物在不同反应温度条件下的加氢产率如图7所示。
实施例9
区别于实施例7，本实施例中使用取样单元实现对生物油样品加氢提质过程的在线监测。取样单元由毛细取样管、蠕动泵组成。取样端口接近催化电极表面，实现对阴极液的在线取样，通过蠕动泵输送收集，然后送至分析仪器，如气相色谱质谱仪、紫外荧光光谱分析仪，可实现对反应产物的原位检测。运行时，通过调整蠕动泵流速实现定时样品采集，采集的样品立即加入甲醇稀释到适配于分析仪器的浓度，然后先后送入紫外荧光光谱分析仪和气相色谱质谱仪进行分析。通过实时的监测，对生物油加氢提质的程度进行评估，并通过电位或、温度或反应时间调节对过程进行调控。
实施例10
区别于实施例7，阴极催化剂直接涂覆在质子交换膜靠近阴极室的一面上(阳极侧不涂)，制成催化剂涂层膜。同时取消催化电极，使导电环直接紧贴交换膜构成新的阴极。将Ru(NH 3) 6Cl 3溶液与5％Nafion溶液混合涂覆在质子交换膜上，形成方形催化剂涂层。省去活性炭布的优点是可以降低阴极导电环和催化剂之间的电阻，一定程度上提高反应的法拉第效率。
上述实施例7－10中，各组件所采用的具体原材料也可用现有技术中已知的具有相同功能的材料替换，例如质子交换膜就可以采用其他现有技术已知的质子交换膜。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (20)

  1. 一种生物油电化学提质方法，其特征在于，包括以下步骤：
    (a)将生物油、有机溶剂和支持电解质三者混合，混合得到的液体作为阴极液备用；其中，所述支持电解质用以提高电导率；
    (b)准备浓度为0.2-1.0mol/L的酸溶液作为阳极液备用；
    (c)采用所述阴极液和所述阳极液组建电化学反应器，向所述阴极液中插入工作电极，所述阳极液中插入阳极电极，所述阴极液与所述阳极液之间通过1个或2个离子交换膜相隔，并能够形成电流回路；
    (d)在所述阴极液一侧通入保护性气体后，通过所述工作电极和所述阳极电极通入电流以进行电化学反应；所述电化学反应是在50-200mA电流条件下反应2-8h，由此即可实现生物油电化学提质。
  2. 如权利要求1所述生物油电化学提质方法，其特征在于，所述步骤(a)中，所述生物油是由农林废弃物生物质在不低于500℃的高温下热解后经过冷凝直接得到的；
    优选的，所述农林废弃物生物质为稻壳、秸秆、食用菌基质、林木枝桠或树皮。
  3. 如权利要求1所述生物油电化学提质方法，其特征在于，所述步骤(a)中，所述有机溶剂为醇类溶剂，优选为甲醇、乙醇、正丙醇或异丙醇的一种或多种；所述阴极液中生物油组分与醇类溶剂组分的质量比满足9:1-4:1。
  4. 如权利要求1所述生物油电化学提质方法，其特征在于，所述步骤(a)中，所述支持电解质为氯化锂(LiCl)、四丁基六氟磷酸盐(Bu 4NPF 6)或四丁基四氟硼酸盐(Bu 4NBF 4)，所述支持电解质在所述阴极液中的浓度为0.1-0.2mol/L。
  5. 如权利要求1所述生物油电化学提质方法，其特征在于，所述步骤(b)中，所述酸为硫酸、盐酸、高氯酸或磷酸。
  6. 如权利要求1所述生物油电化学提质方法，其特征在于，所述步骤(c) 中，所述电化学反应器是基于H型电解池，所述阴极液和所述阳极液分别位于该H型电解池的两侧，中间通过阳离子交换膜隔开。
  7. 如权利要求1所述生物油电化学提质方法，其特征在于，所述步骤(c)中，所述电化学反应器是基于单膜双室电解池或双膜三室电解池；
    当基于单膜双室电解池时，所述阴极液和所述阳极液分别位于该单膜双室电解池的两侧，中间由阳离子交换膜相隔；
    当基于双膜三室电解池时，所述阴极液和所述阳极液分别位于该双膜三室电解池的两侧，通过中间室相连；所述阴极液通过阴离子交换膜与所述中间室相隔，所述阳极液通过阳离子交换膜与所述中间室相隔。
  8. 如权利要求1所述生物油电化学提质方法，其特征在于，所述步骤(c)中，所述阳极电极为铂电极、钌电极、钯电极、或镍电极；
    所述工作电极为金属材料电极或金属材料修饰电极；其中，所述金属材料电极选自镍电极、钌电极、钯电极、铂电极、铜电极、金电极、不锈钢电极；所述金属材料修饰电极是利用金属材料处理基底材料得到的，所述基底材料选自碳纤维布、活性炭布、玻璃碳纤维纸、碳纸、石墨片、泡沫镍，所述金属材料为铁、镍、钌、钯、或铂元素的盐，优选为Fe(NO 3) 3、Ni(NO 3) 2、Ru(NH 3) 6Cl 3、Pd(NO 3) 2或H 2PtCl 6。
  9. 如权利要求8所述生物油电化学提质方法，其特征在于，所述金属材料修饰电极是通过浸渍法、电镀法或水热法处理得到的。
  10. 如权利要求1所述生物油电化学提质方法，其特征在于，所述步骤(d)中，所述保护性气体为氮气或惰性气体；优选的，所述惰性气体为氩气或氦气。
  11. 一种生物油电化学加氢提质装置，其特征在于，包括电解单元、循环单元和加热单元，其中，
    所述电解单元包括阳极室(1)和阴极室(6)，所述阳极室(1)和所述阴极室(6)位于由耐酸材料构成的相对密封的空间内，两者通过质子交换膜(3)相间隔；其中，所述阳极室(1)用于容纳阳极液，所述阴极室(6)用于容纳生物油；所述电解单元能够通过阳极电极(2)和阴极电极向所述阳极室(1)和所述 阴极室(6)提供直流电，使所述阴极室(6)内的生物油进行电化学加氢处理，实现对生物油的提质；
    所述阳极室(1)和所述阴极室(6)的下部均开设有电解液进口(9)，上部均开设有电解液出口(10)；所述循环单元位于所述电解单元的外部，包括生物油循环单元和阳极液循环单元；其中，所述阴极室(6)的电解液进口(9)与电解液出口(10)通过生物油循环单元相连，能够形成封闭的循环回路；所述阳极室(1)的电解液进口(9)与电解液出口(10)通过阳极液循环单元相连，能够形成循环回路；
    所述加热单元用于对所述阴极室(6)内的生物油进行加热，使这些生物油能够在预先设定的温度条件下进行电化学加氢处理。
  12. 如权利要求11所述生物油电化学加氢提质装置，其特征在于，所述加热单元由阴极室加热电阻丝、热电偶、温控器和直流电源组成，其中，所述阴极室加热电阻丝敷设于所述阴极室(6)的背面，用于与所述直流电源相连，并且，用于与该直流电源连接的接头预留在所述阴极室(6)的外部；所述热电偶用于对所述阴极室(6)内的生物油的温度进行检测，所述温控器用于根据所述热电偶检测得到的温度控制所述直流电源输出功率来改变所述阴极室加热电阻丝功率达到控制所述阴极室电解液温度的目的。
  13. 如权利要求11所述生物油电化学加氢提质装置，其特征在于，所述电化学加氢处理是在催化剂条件下进行的，所述阴极电极为导电环(5)，所述导电环(5)通过催化电极(4)与所述质子交换膜(3)相连；优选的，所述催化电极(4)为以活性炭布或碳纸为基底的、且经所述催化剂修饰的电极，所述催化剂为Ru、Pt、Pd、Ni、或Fe元素的盐，优选为Ru(NH 3) 6Cl 3、H 2PtCl 6、Pd(NO 3) 2、Ni(NO 3) 2或Fe(NO 3) 3；
    所述阳极电极为网状金属电极。
  14. 如权利要求11所述生物油电化学加氢提质装置，其特征在于，所述电化学加氢处理是在催化剂条件下进行的，所述阴极电极为导电环(5)，所述导电环(5)直接与所述质子交换膜(3)相连，所述质子交换膜(3)靠近阴极室(6) 的一面上还涂覆有所述催化剂涂层膜，所述催化剂为Ru、Pt、Pd、Ni、或Fe元素的盐，优选为Ru(NH 3) 6Cl 3、H 2PtCl 6、Pd(NO 3) 2、Ni(NO 3) 2或Fe(NO 3) 3；
    所述阳极电极为网状金属电极。
  15. 如权利要求11所述生物油电化学加氢提质装置，其特征在于，所述生物油循环单元包括位于管道上的蠕动泵和生物油储罐，所述阳极液循环单元包括位于管道上的蠕动泵和阳极液储罐；
    所述生物油循环单元还与冷却单元相连，所述冷却单元能够对所述生物油循环单元内的生物油进行冷却处理。
  16. 如权利要求11所述生物油电化学加氢提质装置，其特征在于，所述生物油电化学加氢提质装置还包括取样单元，所述取样单元包括毛细取样管(11)和蠕动泵，该毛细取样管(11)与所述阴极室(6)内部相连，用于在蠕动泵作用下对所述阴极室(6)内的生物油进行取样。
  17. 如权利要求16所述生物油电化学加氢提质装置，其特征在于，所述取样单元还与紫外荧光光谱分析仪和气相色谱质谱仪相连，所述紫外荧光光谱分析仪和所述气相色谱质谱仪用于对所述取样单元取样得到的生物油进行分析。
  18. 如权利要求11所述生物油电化学加氢提质装置，其特征在于，所述耐酸材料为聚四氟乙烯，所述阳极室(1)和所述阴极室(6)分别设置在2块带凹槽的实心聚四氟乙烯块的凹槽内，通过这2块聚四氟乙烯块的拼接配合密封垫片(7)形成相对密封的空间；优选的，所述密封垫片(7)为聚四氟乙烯密封垫片。
  19. 如权利要求11所述生物油电化学加氢提质装置，其特征在于，所述电解液进口(9)分别位于所述阳极室(1)和所述阴极室(6)的底部，所述电解液出口(10)分别位于所述阳极室(1)和所述阴极室(6)的侧面顶端。
  20. 如权利要求11所述生物油电化学加氢提质装置，其特征在于，在所述阳极室(1)和所述阴极室(6)的底部均设置有迷宫式扰流结构。
PCT/CN2021/083454 2020-07-29 2021-03-27 一种生物油电化学提质方法及生物油电化学加氢提质装置 Ceased WO2022021909A1 (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN202010745427.XA CN111871350B (zh) 2020-07-29 2020-07-29 一种生物油电化学加氢提质装置
CN202010745400.0A CN111909736B (zh) 2020-07-29 2020-07-29 一种生物油电化学提质方法
CN202010745427.X 2020-07-29
CN202010745400.0 2020-07-29

Publications (1)

Publication Number Publication Date
WO2022021909A1 true WO2022021909A1 (zh) 2022-02-03

Family

ID=80037463

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/083454 Ceased WO2022021909A1 (zh) 2020-07-29 2021-03-27 一种生物油电化学提质方法及生物油电化学加氢提质装置

Country Status (1)

Country Link
WO (1) WO2022021909A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118792666A (zh) * 2024-09-14 2024-10-18 华澳得塔氢能科技(天津)有限公司 一种用于从生物质及其衍生分子合成燃料的电催化反应器
CN119500023A (zh) * 2025-01-22 2025-02-25 东南大学 基于soec的生物质热解蒸气一体化耦合在线提质系统和工艺
CN121023554A (zh) * 2025-10-23 2025-11-28 浙江奕湃科技有限公司 一种一体化膜电极及其制备方法与用于蒽醌衍生化合物定向还原氧化调控合成过氧化氢的装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013134220A1 (en) * 2012-03-06 2013-09-12 Board Of Trustees Of Michigan State University Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds
CN103497843A (zh) * 2013-10-12 2014-01-08 东北农业大学 一种超临界co2添加h2条件下电氢化大豆油脂的方法
CN108660477A (zh) * 2018-04-19 2018-10-16 中国华能集团清洁能源技术研究院有限公司 一种5-羟甲基糠醛在质子交换膜反应器中电催化加氢制备二甲基呋喃的方法
CN111871350A (zh) * 2020-07-29 2020-11-03 华中科技大学 一种生物油电化学加氢提质装置
CN111909736A (zh) * 2020-07-29 2020-11-10 华中科技大学 一种生物油电化学提质方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013134220A1 (en) * 2012-03-06 2013-09-12 Board Of Trustees Of Michigan State University Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds
CN103497843A (zh) * 2013-10-12 2014-01-08 东北农业大学 一种超临界co2添加h2条件下电氢化大豆油脂的方法
CN108660477A (zh) * 2018-04-19 2018-10-16 中国华能集团清洁能源技术研究院有限公司 一种5-羟甲基糠醛在质子交换膜反应器中电催化加氢制备二甲基呋喃的方法
CN111871350A (zh) * 2020-07-29 2020-11-03 华中科技大学 一种生物油电化学加氢提质装置
CN111909736A (zh) * 2020-07-29 2020-11-10 华中科技大学 一种生物油电化学提质方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LAM CHUN HO, DENG WEI, LANG LIN, JIN XIN, HU XUN, WANG YI: "Minireview on Bio-Oil Upgrading via Electrocatalytic Hydrogenation: Connecting Biofuel Production with Renewable Power", ENERGY & FUELS, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US., vol. 34, no. 7, 16 July 2020 (2020-07-16), WASHINGTON, DC, US. , pages 7915 - 7928, XP055891000, ISSN: 0887-0624, DOI: 10.1021/acs.energyfuels.0c01380 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118792666A (zh) * 2024-09-14 2024-10-18 华澳得塔氢能科技(天津)有限公司 一种用于从生物质及其衍生分子合成燃料的电催化反应器
CN119500023A (zh) * 2025-01-22 2025-02-25 东南大学 基于soec的生物质热解蒸气一体化耦合在线提质系统和工艺
CN121023554A (zh) * 2025-10-23 2025-11-28 浙江奕湃科技有限公司 一种一体化膜电极及其制备方法与用于蒽醌衍生化合物定向还原氧化调控合成过氧化氢的装置

Similar Documents

Publication Publication Date Title
CN111909736B (zh) 一种生物油电化学提质方法
Sun et al. Investigations on degradation of the long-term proton exchange membrane water electrolysis stack
CN108193225B (zh) 一种膜电极构型co2电还原电解池
Song et al. Aqueous phase electrocatalysis and thermal catalysis for the hydrogenation of phenol at mild conditions
WO2022021909A1 (zh) 一种生物油电化学提质方法及生物油电化学加氢提质装置
CN111871350B (zh) 一种生物油电化学加氢提质装置
CN105200448B (zh) 一种有机物脱氢与加氢耦合的电化学氢泵双反应器
KR20130037649A (ko) 막 전극 접합체 및 유기 하이드라이드 제조 장치
CN116288458B (zh) 一种碱性膜电解水制氢膜电极及基于其的电解水制氢装置
CN112481656A (zh) 高选择性电催化甘油氧化转化产甲酸和高效电解水产氢的双功能催化剂及其制备方法与应用
CN113512736B (zh) 一种电化学沉积制备膜电极的方法及其应用
Zhao et al. Electrocatalytic hydrogenation of lignin-derived phenol into alkanes by using platinum supported on graphite
CN117004970B (zh) 一种基于有机液体电化学加氢的pem反应器及其系统
Kawaguchi et al. Upgrading of Ethanol to 1, 1‐Diethoxyethane by Proton‐Exchange Membrane Electrolysis
CN103123974A (zh) 导电聚合物/金属/质子交换膜型复合膜及其制备和应用
CN113373464B (zh) 一种电催化转化木质素衍生物制备环烷烃的方法
Grimaldos-Osorio et al. From plastic-waste to H2: Electrolysis of a Poly (methyl methacrylate) model molecule on polymer electrolyte membrane reactors
CN115584517A (zh) 一种电催化生产甲酸的单室电解系统的方法
Yuan et al. Converting CO2 to multi-carbon products at> 1 A/cm2 using gas diffusion electrode based on commercial materials via transfer process engineering
Ding et al. Performance improvement of the liquid-fed SO2-depolarized electrolyzers for anolyte with high H2SO4 concentration
Lamy et al. A kinetics analysis of methanol oxidation under electrolysis/fuel cell working conditions
Ma et al. Application of Pt loaded graphite felt in SO2-depolarized electrolyzer
CN102389823A (zh) 一种高利用率燃料电池催化剂的制备方法
Chiu et al. Self-catalyzed NiFe foam anode fabricated via tape-casting for oxygen evolution reaction in anion exchange membrane water electrolysis
Ji et al. In situ electrosynthesis of quinone-based redox-active molecules coupling with high-purity hydrogen production

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21849558

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21849558

Country of ref document: EP

Kind code of ref document: A1