CN113713734B - Method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil - Google Patents

Method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil Download PDF

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CN113713734B
CN113713734B CN202110931038.0A CN202110931038A CN113713734B CN 113713734 B CN113713734 B CN 113713734B CN 202110931038 A CN202110931038 A CN 202110931038A CN 113713734 B CN113713734 B CN 113713734B
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pyrolysis oil
precursor solution
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reaction
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CN113713734A (en
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汪一
邓伟
熊哲
汪雪棚
陈元静
向军
胡松
苏胜
江龙
徐俊
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Huazhong University of Science and Technology
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
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Abstract

The invention belongs to the field of biomass energy utilization, and discloses a method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil, which comprises the following steps: (S1) obtaining a precursor solution by using the biomass pyrolysis oil; (S2) charging the precursor solution into the electrochemical reactor while inserting the electrode; (S3) starting an electrochemical reaction to form a micro-nano spherical structure of the carbon-containing component in the biomass pyrolysis oil; simultaneously, cleaning the solid attachments attached to the surface of the electrode obtained by reaction to a precursor solution phase according to a preset time interval; (S4) collecting the solution phase of the precursor after reaction, performing solid-liquid separation to collect solid, and drying to obtain the product micro-nano carbon spheres. The invention can effectively solve the problems of low yield of carbon material products obtained from the biomass oil by improving the process design of the whole process of the method and the like, and can prepare the micro-nano carbon spheres by using the biomass pyrolysis oil as a raw material by adopting an electrochemical reaction process with mild conditions.

Description

Method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil
Technical Field
The invention belongs to the field of biomass energy utilization, and particularly relates to a method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil.
Background
The widespread use of renewable energy is considered as a fossil energy alternative to promote economic development, secure energy supply, and alleviate global warming. The biomass energy resources are widely distributed and abundant in reserves, and are the only carbon-containing renewable resources. China has used biomass resource utilization as a comprehensive strategy and aims to realize the goal in 2060 carbon and the vogue of villages. The biomass can be converted into pyrolysis gas, pyrolysis coke and pyrolysis oil by a pyrolysis poly-generation technology, the pyrolysis gas, the pyrolysis coke and the pyrolysis oil can be directly used as fuel and a soil corrosion inhibitor respectively, and the pyrolysis oil is difficult to directly use due to complex components, high oxygen content, high viscosity, poor thermal stability and easy polymerization and coking under heating, and can be further used only by being converted into products with high fuel property and high added value through upgrading. Currently, the pyrolysis oil upgrading method is mainly a thermochemical method such as catalytic cracking, hydrodeoxygenation, reforming, and the like. However, the pyrolysis oil has poor thermal stability, and is easy to generate polymerization reaction to generate carbon deposition when being heated, so that a reaction device, a pipeline are blocked, and a catalyst is inactivated, thereby greatly reducing the upgrading efficiency and the operation stability. Therefore, some researchers propose a biomass pyrolysis oil utilization mode for preparing a carbon material by utilizing the characteristic that pyrolysis oil is easy to coke when being heated. Elliot et al studied the production of electrodes from coke using biomass pyrolysis oil. Hu et al developed a method for producing a high strength carbonaceous material from pyrolysis oil and pyrolysis coke as raw materials. However, one of the major challenges in producing carbon materials using thermochemical methods is the release of large amounts of volatiles during heat treatment resulting in carbon loss, resulting in low yields of carbon material product (less than 30%). Electrochemical methods can overcome this problem with their low temperature advantage. In fact, the use of electrochemical methods in polymerization dates back to 1949, where Wilson et al studied the polymerization behavior of acrylic acid and methyl methacrylate. Subsequently, a great deal of research work has been continuously conducted to expand the electrochemical polymerization technology to the synthesis of polymers and develop various technologies. Electrochemistry has become an effective way to prepare conducting polymers. However, at present, there is no research on the electrochemical production of carbon materials using biomass pyrolysis oil as a raw material. Therefore, the invention provides a brand new technical route for preparing the micro-nano carbon spheres by using the biomass pyrolysis oil based on the normal-temperature process of electrochemical reaction, skillfully solves the difficult problem that coking of the pyrolysis oil is difficult to avoid, and can realize high-value resource utilization of the biomass pyrolysis oil.
Disclosure of Invention
The above deficiencies and needs in the art are addressed and improved by the present inventionThe invention provides a method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil, wherein the overall process design of the method is improved, electrochemical reaction and dehydration and decarboxylation effects brought by the electrochemical reaction are utilized, and key parameter conditions (such as current density interval and electrode cleaning interval time) of the electrochemical reaction are preferably controlled. Moreover, the invention can especially control the current density of the electrochemical reaction to be 50-200mAcm -2 And the yield is high, and the efficient preparation of the micro-nano carbon spheres can be realized.
In order to achieve the purpose, the invention provides a method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil, which is characterized by comprising the following steps of:
(S1) adding an organic solvent and a supporting electrolyte into the biomass pyrolysis oil, and uniformly mixing to obtain a precursor solution;
(S2) charging the precursor solution into an electrochemical reactor while inserting an electrode into the precursor solution; wherein the electrode is capable of providing a voltage difference to the precursor solution to carry out an electrochemical reaction;
(S3) after protective gas is introduced into the electrochemical reactor, starting electrochemical reaction, removing oxygen element in the biomass pyrolysis oil through dehydration and decarboxylation effects brought by the electrochemical reaction, increasing the carbon content in the biomass pyrolysis oil, and enabling carbon-containing components in the biomass pyrolysis oil to be stacked in a carbon-carbon single bond form to form a micro-nano spherical structure under the surface energy minimization effect; in the reaction process of the electrochemical reaction, cleaning a solid attachment attached to the surface of an electrode obtained by the reaction to a precursor solution phase through a mechanical mode or a mode of changing the voltage direction according to a preset time interval;
(S4) after the electrochemical reaction is finished, collecting the precursor solution phase after the reaction, carrying out solid-liquid separation, collecting the solid, and drying to obtain the product micro-nano carbon spheres, wherein the size of the micro-nano carbon spheres is 50nm-5 μm.
As a further preferred aspect of the present invention, in the step (S3), the solid attachments attached to the surface of the electrode obtained by the reaction are cleaned to the solution phase of the precursor by specifically changing the voltage direction;
in the step (S3), the electrochemical reaction is at 50-200mAcm -2 The current density is carried out under the condition of a preset time interval of 7-30 min;
preferably:
when the current density is 50-100mAcm -2 The preset time interval is 20-30 min;
when the current density is 100-150mAcm -2 The preset time interval is 10-20 min;
when the current density is 150-200mAcm -2 The preset time interval is 7-10 min.
As a further preferable mode of the present invention, in the step (S1), the biomass pyrolysis oil is directly obtained by condensing after pyrolyzing agricultural and forestry waste biomass at a temperature of not less than 500 ℃;
preferably, the agricultural and forestry waste biomass is at least one of rice hulls, straws, edible fungus matrixes, forest branches and barks.
As a further preferred aspect of the present invention, in the step (S1), the organic solvent is an alcohol solvent, preferably one or more of methanol, ethanol, n-propanol or isopropanol; the mass ratio of the alcohol solvent in the precursor solution is 5.0-10.0%.
As a further preferred aspect of the present invention, in the step (S1), the supporting electrolyte is lithium chloride (LiCl) or tetrabutyl hexafluorophosphate (Bu) 4 NPF 6 ) Or tetrabutyltetrafluoroborate (Bu) 4 NBF 4 ) And the concentration of the supporting electrolyte in the precursor solution is 0.1-0.2 mol/L.
As a further preferred aspect of the present invention, in the step (S2), the electrode is a metal electrode; the metal material electrode is selected from a nickel electrode, a ruthenium electrode, a palladium electrode, a platinum electrode, a copper electrode, a gold electrode and a stainless steel electrode.
As a further preferred aspect of the present invention, in the step (S2), the electrochemical reactor is a single-chamber electrolytic cell, more preferably a continuous flow single-chamber electrolytic cell.
As a further preferred aspect of the present invention, in the step (S3), the total time of the electrochemical reaction is 6 to 10 hours;
the protective gas is nitrogen or inert gas; preferably, the inert gas is argon or helium;
the preset time interval is specifically 10-30 min; preferably, the mechanical means comprises direct scraping or electrode vibration.
As a further preferred aspect of the present invention, in the step (S4), the solid is further derived from: washing the inner wall of the electrochemical reactor and the surface of the electrode by adopting absolute methanol or absolute ethanol, and then carrying out solid-liquid separation on the washed solution to obtain a solid;
preferably, the solid-liquid separation is suction filtration separation or centrifugal separation.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a brand new technical scheme for preparing micro-nano carbon spheres by using biomass pyrolysis oil based on electrochemistry, and the resource high-value utilization of biomass can be realized. According to the method, the biomass pyrolysis oil is used as a raw material, an electrochemical reaction is utilized, and the dehydration and decarboxylation effects brought by the electrochemical reaction are utilized to remove oxygen elements in the biomass pyrolysis oil, so that the carbon content in the biomass pyrolysis oil is improved, carbon-containing components in the biomass pyrolysis oil are accumulated in a carbon-carbon single bond form, a micro-nano spherical structure is formed under the surface energy minimization effect, and micro-nano carbon spheres (such as micro-nano carbon spheres with the particle size of 50nm-5 mu m, and the like, can be prepared, wherein the particle size is larger when the current density is increased and the reaction time is increased).
(2) The biomass pyrolysis oil is full of components, the pyrolysis oil does not need to be separated in advance, and the process is simple. For example, based on the method of the present invention, biomass pyrolysis oil directly obtained by condensing agriculture and forestry waste biomass (such as rice hulls, straws, edible fungus matrixes, forest branches, barks, etc.) after pyrolysis at a temperature of not less than 500 ℃ is used as a raw material, and the raw material is mixed with an organic solvent and a supporting electrolyte to obtain a precursor solution, and then the precursor solution is subjected to subsequent electrochemical treatment.
(3) The electrochemical reaction in the invention can be implemented at normal temperature (such as 20-25 ℃, and certainly at other temperatures of 20-60 ℃) and normal pressure (namely, one standard atmospheric pressure), and the volatilization amount of the pyrolysis oil is very low in the electrochemical reaction process, so that the biomass-based carbon component in the pyrolysis oil is retained to the maximum extent and is converted into the micro-nano carbon spheres, which is different from the conditions of high temperature and high pressure.
(4) The precursor solution prepared by the invention comprises organic solvent and supporting electrolyte besides biomass pyrolysis oil, and takes the organic solvent as an alcohol solvent as an example, and the mass proportion of the alcohol solvent in the precursor solution is 5.0-10.0%; in consideration of the actual conditions that the pyrolysis oil has low conductivity and the supporting electrolyte has low solubility in the pyrolysis oil, the concentration of the supporting electrolyte in the precursor solution can be particularly preferably 0.1-0.2mol/L, so that the conductivity of the precursor solution can be effectively improved and controlled within the preferable range of 1.2-2.4S/cm; in addition, the invention can particularly use the same alcohol solvent (such as methanol, ethanol, normal propyl alcohol, isopropanol and the like) as the alcohol component contained in the pyrolysis oil, and can reduce the influence of the added component on the component of the pyrolysis oil to the maximum extent.
(5) According to the invention, the solid attachments on the surface of the anode electrode are preferably removed by changing the voltage direction, the anode where the solid attachments are located is temporarily changed into the cathode by changing the polarity of the electrode, so that the surface of the anode generates hydrogen evolution reduction reaction, and the solid attachments are flushed down by a gas evolution bubbling mode. The invention can particularly adopt a single-chamber electrolytic cell as an electrochemical reactor, and can realize the high-efficiency electrochemical treatment of the biomass pyrolysis oil by using membraneless electrolysis in combination with the change of the voltage direction in the electrochemical reaction process.
(6) The electrochemical reaction in the invention preferably adopts a reaction current density interval of 50-200mAcm -2 The micro-nano carbon sphere product with better current efficiency, product appearance and yield can be realized. Generally, the current efficiency increases first with increasing current density, reaching a maximum value and then beginning to decrease; the method of the invention adopts 50-200mAcm -2 The current efficiency can be maintained above 45% within the current density range, and the highest current efficiency can reach 82%. Further, when the current density is less than 50mAcm -2 When the method is used, the amount of solid products formed on the surface of the electrode is small, and the content of the micro-nano carbon sphere structure with the size of 50nm-5 mu m is small, so that the yield of the micro-nano carbon spheres is reduced; when the current density is more than 200mAcm -2 In the process, gas is violently separated out from the electrode due to high overpotential, and a formed solid product layer is loose and uneven, so that the yield of the micro-nano carbon spheres is reduced. In general, the present invention preferably uses 50-200mAcm -2 For optimal reaction current density.
(7) Further, with 50-200mAcm -2 The current density is matched, the method can clean the solid attachments attached to the surface of the electrode obtained by reaction into a precursor solution phase every 10-30min, and the electrode is cleaned, so that the high-efficiency preparation of the micro-nano carbon spheres is realized. Considering that the adsorption state reaction substance sites on the surface of the electrode are saturated along with the continuous reaction, the yield is not increased even if the reaction time is continuously increased, and therefore, the yield can be effectively ensured by regularly cleaning the electrode. In addition, the higher the current density adopted is, the shorter the reaction time required for forming the micro-nano carbon spheres is, so the invention can particularly adopt the following electrode cleaning time interval setting: when the current density is 50-100mAcm -2 The reaction time interval is 20-30 min; when the current density is 100-150mAcm -2 The reaction time interval is 10-20 min; when the current density is 150-200mAcm -2 And the reaction time interval is 7-10min, so that the high-efficiency preparation of the micro-nano carbon spheres is realized.
Drawings
FIG. 1 is a schematic flow diagram of a method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil.
FIG. 2 is a scanning electron microscope image of the micro-nano carbon spheres prepared in example 1 of the present invention; the scale in the figure represents 10 μm.
FIG. 3 is a scanning electron microscope image of the micro-nano carbon spheres prepared in example 5 of the present invention; the scale in the figure represents 500 nm.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The embodiment specifically comprises the following steps:
(a) adding 0.1mol/L LiCl supporting electrolyte into methanol, mixing biomass pyrolysis oil and the methanol according to the mass ratio of 19:1, and taking the mixed liquid as a precursor solution for later use; the pyrolysis oil is obtained by pyrolyzing rice hulls at 600 ℃.
(b) Preparing a single-chamber electrolytic cell, filling a precursor solution into the electrolytic cell, and inserting two electrodes, namely an anode electrode and a cathode electrode, into the solution to form a current loop; in this example, a platinum sheet was used as a cathode electrode, a platinum wire was used as an anode electrode, and the surface areas of the platinum sheet and the platinum wire were 1cm 2 The electrodes are connected by a direct current power supply;
(c) introducing nitrogen into the electrolytic cell for 15min, turning on a direct current power supply, and keeping the current density at 50mAcm -2 And the reaction temperature is 25 ℃, and a current loop is switched on through the anode electrode and the cathode electrode to start the electrochemical preparation process.
(d) In the electrochemical preparation process, the solid attachments on the surface of the anode are regularly cleaned into a precursor solution phase by changing the voltage direction, the interval time of cleaning the timing electrode is set to be 30min, and the total time length of the electrochemical preparation process is set to be 10 h.
(e) And after the electrochemical preparation process is finished, collecting the precursor solution after the reaction for solid-liquid separation, cleaning the inner wall of the electrochemical reactor and the surface of an electrode by adopting absolute ethyl alcohol, carrying out solid-liquid separation on the solution after cleaning, collecting the solid, and freeze-drying for 24 hours at the temperature of 50 ℃ below zero and under the condition of 10Pa to obtain the product, namely the micro-nano carbon spheres. The scanning electron microscope picture of the obtained micro-nano carbon spheres is shown in figure 2, the particle size is uniform, and the particle size of most carbon spheres is 1-2 mu m. The mass of the collected micro-nano carbon spheres is about 64% of the mass of the pyrolysis oil filled in the electrochemical reactor.
Example 2
The current density used in this example was 150mAcm -2 The timing electrode cleaning interval time was set to 10min, and the remaining conditions were the same as in example 1. The mass of the collected micro-nano carbon spheres is about 77% of the mass of the pyrolysis oil filled in the electrochemical reactor, and the particle size of most carbon spheres is 2-3 μm.
Example 3
The current density used in this example was 200mAcm -2 The timing electrode cleaning interval time was set to 7min, and the remaining conditions were the same as in example 1. The mass of the collected micro-nano carbon spheres is about 67 percent of the mass of the pyrolysis oil filled in the electrochemical reactor, and the grain diameter of most carbon spheres is 2-3 mu m.
Example 4
In this example, the biomass pyrolysis oil and methanol were mixed at a mass ratio of 9:1, and the remaining conditions were the same as in example 1. The mass of the collected micro-nano carbon spheres is about 51 percent of the mass of the pyrolysis oil filled in the electrochemical reactor, and the grain diameter of most carbon spheres is 1-2 mu m.
Example 5
The current density used in this example was 100mAcm -2 The timing electrode cleaning interval time was set to 10min, biomass pyrolysis oil and methanol were mixed in a mass ratio of 9:1, and the remaining conditions were the same as in example 1. The scanning electron microscope picture of the obtained micro-nano carbon spheres is shown in figure 3, and the mass of the collected micro-nano carbon spheres is about the mass of the pyrolysis oil filled in the electrochemical reactor57% of the total carbon spheres, and the particle size of most carbon spheres is 50-300 nm.
The above embodiments are merely examples, and other specific materials may be used to implement the present invention based on the method of the present invention. For example, the supporting electrolyte used to increase the conductivity may be made of other supporting electrolyte materials (e.g., Bu) known in the art, in addition to the specific materials used in the above examples 4 NPF 6 、Bu 4 NBF 4 Etc.); for example, in addition to alcohol solvents, n-hexane, benzene, etc. can be used as an organic solvent in the present invention; besides the mode of changing the voltage direction, mechanical methods such as direct scraping, electrode vibration and the like can be adopted for cleaning the solid attachments on the surface of the anode. In addition, besides the electrochemical reaction realized by a two-electrode system, a three-electrode system can be adopted, and the invention is not illustrated.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (11)

1. A method for electrochemically preparing micro-nano carbon spheres by using biomass pyrolysis oil is characterized by comprising the following steps:
(S1) adding an organic solvent and a supporting electrolyte into the biomass pyrolysis oil, and uniformly mixing to obtain a precursor solution; wherein the organic solvent is an alcohol solvent, and the mass ratio of the alcohol solvent in the precursor solution is 5.0-10.0%;
(S2) charging the precursor solution into an electrochemical reactor while inserting an electrode into the precursor solution; wherein the electrode is capable of providing a voltage difference to the precursor solution to carry out an electrochemical reaction;
(S3) after protective gas is introduced into the electrochemical reactor, starting electrochemical reaction, removing oxygen element in the biomass pyrolysis oil through dehydration and decarboxylation effects brought by the electrochemical reaction, increasing the carbon content in the biomass pyrolysis oil, and enabling carbon-containing components in the biomass pyrolysis oil to be stacked in a carbon-carbon single bond form to form a micro-nano spherical structure under the surface energy minimization effect; in the reaction process of the electrochemical reaction, cleaning the solid attachments attached to the surface of the electrode obtained by the reaction into a precursor solution phase by changing the voltage direction according to a preset time interval;
(S4) after the electrochemical reaction is finished, collecting a precursor solution phase after the reaction, carrying out solid-liquid separation, collecting solids, and drying to obtain a product micro-nano carbon sphere, wherein the size of the micro-nano carbon sphere is 50nm-5 μm;
wherein, in the step (S3), the electrochemical reaction is in the range of 50-200mAcm -2 Under the condition of current density;
when the current density is 50-100mAcm -2 The preset time interval is 20-30 min;
when the current density is 100-150mAcm -2 The preset time interval is 10-20 min;
when the current density is 150-200mAcm -2 The preset time interval is 7-10 min.
2. The method according to claim 1, wherein in the step (S1), the biomass pyrolysis oil is directly obtained by condensing agriculture and forestry waste biomass after pyrolysis at a temperature of not less than 500 ℃.
3. A method as claimed in claim 2, wherein said agricultural and forestry waste biomass is at least one of rice hulls, straw, edible fungus substrate, tree branches, and bark.
4. The method according to claim 1, wherein in the step (S1), the organic solvent is one or more of methanol, ethanol, n-propanol or isopropanol.
5. The method according to claim 1, wherein in the step (S1), the supporting electrolyte is lithium chloride (LiCl), tetrabutyl hexafluorophosphate or tetrabutyl tetrafluoroborate, and the concentration of the supporting electrolyte in the precursor solution is 0.1 to 0.2 mol/L.
6. The method according to claim 1, wherein in the step (S2), the electrode is a metal material electrode; the metal material electrode is selected from a nickel electrode, a ruthenium electrode, a palladium electrode, a platinum electrode, a copper electrode, a gold electrode and a stainless steel electrode.
7. The method of claim 1, wherein in said step (S2), said electrochemical reactor is a single-chamber electrolytic cell.
8. The method of claim 7, wherein in step (S2), the electrochemical reactor is a continuous flow single chamber electrolytic cell.
9. The method according to claim 1, wherein in the step (S3), the total time of the electrochemical reaction is 6-10 h;
the protective gas is nitrogen or inert gas.
10. The method of claim 9, wherein the inert gas is argon or helium.
11. The method of claim 1, wherein in step (S4), the solids are further derived from: washing the inner wall of the electrochemical reactor and the surface of the electrode by using absolute methanol or absolute ethanol, and then carrying out solid-liquid separation on the washed solution to obtain a solid;
the solid-liquid separation is suction filtration separation or centrifugal separation.
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