CN113249142A - Preparation method of biomass charcoal-metal oxide composite electrode material - Google Patents

Preparation method of biomass charcoal-metal oxide composite electrode material Download PDF

Info

Publication number
CN113249142A
CN113249142A CN202110561067.2A CN202110561067A CN113249142A CN 113249142 A CN113249142 A CN 113249142A CN 202110561067 A CN202110561067 A CN 202110561067A CN 113249142 A CN113249142 A CN 113249142A
Authority
CN
China
Prior art keywords
biomass
metal oxide
electrode material
oxide composite
composite 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.)
Pending
Application number
CN202110561067.2A
Other languages
Chinese (zh)
Inventor
张建波
杨文成
杨恩
蒋盼盼
马晓迅
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.)
Shaanxi Coal and Chemical Technology Institute Co Ltd
Northwestern University
Original Assignee
Northwestern University
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
Application filed by Northwestern University filed Critical Northwestern University
Priority to CN202110561067.2A priority Critical patent/CN113249142A/en
Publication of CN113249142A publication Critical patent/CN113249142A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C10J3/56—Apparatus; Plants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam

Abstract

The invention provides a preparation method of a biomass charcoal-metal oxide composite electrode material, which realizes the graded conversion and utilization of biomass resources by regulating and controlling the processes of catalytic pyrolysis of biomass, partial gasification reaction of pyrolysis semicoke and the like, and can obtain the beneficial effects of co-producing high-calorific-value fuel gas, biomass oil and high-performance biomass charcoal-metal oxide composite electrode material. The method provided by the invention has simple design, prolongs the industrial chain of biomass conversion and has good industrial application prospect.

Description

Preparation method of biomass charcoal-metal oxide composite electrode material
Technical Field
The invention belongs to the field of conversion processing of biomass chemical engineering or low-carbon resources, and particularly relates to a preparation method of a biomass charcoal-metal oxide composite electrode material.
Background
The biomass is a carbon-neutral renewable energy source, has wide sources and low cost, is developed in the future by reasonable and efficient utilization, and plays a considerable role in solving environmental problems and resource crisis. The biomass charcoal is a porous carbon material rich in carbon elements, can be generally prepared by thermally converting agricultural and forestry wastes (corncobs, rice husks, wheat straws, wood chips and the like) or organic solid wastes (sludge, food wastes and the like), and has related application reports in the fields of catalysis, gas purification, energy storage and the like.
Biomass pyrolysis is a relatively common thermal conversion process, and is generally a process of thermally decomposing biomass (the operation temperature is generally 350-. Wherein the gaseous product consists essentially of CO2、CO、H2And CH4And the like. The solid product is mainly biomass semicoke containing a small amount of inorganic minerals.
Biomass gasification is another common thermal conversion process, generally requiring higher temperature (550-2And CO) gas. The gasifying agent generally comprises CO2Water vapor, O2Or air. Wherein the greenhouse gas CO is utilized2As a gasifying agent, CO in industrial waste gas can be recycled2Generating combustible gas CO and realizing the value increment of fuel gas. In addition, with water vapor or O2By contrast, CO2When the biomass gasification agent is used as a gasification agent for biomass gasification, the gasification reaction is mild, and the biomass-based porous carbon is obtained by partial gasification operation. When the water vapor is used as the gasifying agent, the raw material source is convenient, and the gasification reaction rate is higher (compared with CO)2Gasification) but with higher energy consumption (relative to CO)2Gasified). O is2Or when air is used as a gasifying agent, the gasification reaction intensity is severe, and the carbon residue rate of the residue is obviously reduced. Wherein air (containing about 78% N)2And 21% of O2) When used as a gasifying agent, a large amount of N is mixed in the gas released by the gasification reaction2The heat value of the gasification tail gas can be obviously reduced, and the difficulty of tail gas separation is increased.
The super capacitor has the advantages of both a conventional capacitor and a common battery, and is an important energy storage device. The novel lithium ion battery has the characteristics of rapid charge and discharge, wide temperature application range, charge and discharge cycle stability of thousands of times and the like, and has wide development prospect and application market. But the performance of its electrode material has a decisive influence on the electrochemical performance of the supercapacitor. Currently, the electrode materials studied more mainly include three main types: conductive polymers, carbon materials, and transition metal oxides. Different materials have their own advantages and disadvantages.
Disclosure of Invention
The invention provides a preparation method of a biomass charcoal-metal oxide composite electrode material, which realizes the graded conversion and utilization of biomass resources.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a biomass charcoal-metal oxide composite electrode material comprises the following steps:
drying a biomass raw material, and then crushing the biomass raw material into biomass particles;
adding the biomass particles and a metal salt reagent into an organic matter-water solution, uniformly mixing, drying, and then pyrolyzing at 350-550 ℃ for 30-100 minutes under the protection of pyrolysis atmosphere to produce pyrolysis gas, biomass oil and metal-loaded pyrolysis semicoke;
and step three, carrying out gasification reaction on the metal-loaded pyrolysis semicoke produced in the step two under the action of a gasification agent to obtain the biomass carbon-metal oxide composite electrode material.
The further improvement of the invention is that in the first step and the second step, the drying temperature is 100-110 ℃, and the particle size of the biomass particles is 100-300 mu m.
The invention has the further improvement that in the step one, the biomass raw material is pine sawdust, corn straw, peanut shells or walnut shells.
The further improvement of the invention is that in the second step, the metal salt reagent is any one or more of nickel nitrate, ferric nitrate, cobalt nitrate and manganese nitrate.
The further improvement of the invention is that in the second step, the organic matter-water solution is a mixture of any one or more of methanol, ethanol, isopropanol, acetone, cyclohexanone, diethyl ether and propylene oxide and water.
The further improvement of the invention is that in the second step, the dosage of the biomass particles and the metal salt reagent is calculated according to the mass ratio of the biomass particles to the metal simple substance in the metal salt reagent (10-200): 1.
The further improvement of the invention is that in the second step, the pyrolysis atmosphere is any one or more of hydrogen, synthesis gas, pyrolysis gas and methane.
The further improvement of the invention is that in the third step, the gasifying agent is any one or more of water vapor, carbon dioxide, air and oxygen.
The further improvement of the invention is that in the third step, the gasification reaction process is as follows: under normal pressure or micro-positive pressure, at a temperature of 700-900 ℃ and an initial reaction space velocity of 1-100L/(g)Semi-cokeH), carrying out constant-temperature reaction for 0.5-3 h in a fixed bed or fluidized bed reactor.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel process technology for co-producing high-calorific-value fuel gas, biomass oil and biomass charcoal-metal oxide composite electrode material by utilizing catalytic pyrolysis of biomass raw materials and partial gasification reaction of pyrolysis semicoke. Compared with the traditional technology for preparing electrode materials by using biomass, the method has the advantages that the variety of obtained products is multiple, the graded conversion and utilization of the biomass are realized, and the problems of low energy effective utilization efficiency, poor economy and the like in the traditional technology are effectively solved. According to the invention, the biomass is subjected to drying, crushing, catalytic pyrolysis, partial gasification reaction of pyrolysis semicoke and other operation steps, and the process conditions are regulated and optimized, so that the graded conversion and utilization of biomass resources are realized, and the beneficial effects of co-producing high-calorific-value fuel gas, biomass oil and high-performance biomass charcoal-metal oxide composite electrode material can be obtained. The preparation method provided by the invention is simple, prolongs the industrial chain of biomass conversion, and has good industrial application prospect. Compared with the traditional biomass pyrolysis technology, the technical scheme provided by the invention introduces the metal catalyst (the pyrolysis temperature can be utilized to realize the decomposition of the metal salt reagent and form the metal oxide, so that the metal oxide catalyst is formed), the heat value of the fuel gas can be improved, the lightening of the biomass oil can be promoted, and meanwhile, the oxygen-containing functional groups on the surface of the biomass can be utilized to promote the formation of the highly dispersed metal oxide loaded by the biomass semicoke. Compared with the traditional biomass semicoke gasification technology, the biomass semicoke in the technical scheme provided by the invention is the biomass semicoke loaded with highly dispersed metal oxide, and in the gasification process, the metal oxide can play a role of a catalyst to promote the gasification reaction of a carbon substrate in the biomass semicoke and improve the porosity and the specific surface area of the biomass semicoke.
Drawings
Fig. 1(a) is a scanning electron microscope image of the biomass char-metal oxide composite prepared under the operating conditions of example 1.
FIG. 1(b) is a scanning electron micrograph of a biomass porous carbon material prepared under the operating conditions of example 1.
Fig. 2 is an XPS plot of biomass char-metal oxide composite prepared under the operating conditions of example 1.
Fig. 3(a) is a cyclic voltammogram of biomass char-metal oxide composite prepared under the operating conditions of example 1 at different scan rates.
Fig. 3(b) is a constant current charge and discharge curve of the biomass char-metal oxide composite prepared under the operating conditions of example 1 at different current densities.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but is not limited to the following examples.
Although the proposal of the invention also produces synthesis gas (mixture of hydrogen and carbon monoxide), the target product is not shown here, but the composite electrode material of biomass-based porous carbon-supported metal oxide is obtained by controlling the degree of gasification reaction.
A preparation method of a biomass charcoal-metal oxide composite electrode material comprises the following steps:
step one, drying and crushing biomass raw materials: the biomass raw material needs to be dried in advance at the temperature of 100-110 ℃, and then is crushed into small particles with the particle size of 100-300 mu m.
Step two, catalytic pyrolysis of biomass: the dried and crushed biomass particles and a metal salt reagent are weighed according to a certain mass ratio, placed into a prepared organic matter-water solution for stirring and mixing, and then dried at 100-110 ℃ in sequence, and pyrolyzed at 350-550 ℃ for 30-100 minutes under the protection of a certain pyrolysis atmosphere to produce pyrolysis gas, biomass oil and metal-loaded pyrolysis semicoke.
Step three, partial gasification reaction of pyrolysis semicoke: and (3) carrying out gasification reaction on the pyrolysis semicoke produced in the step two under the action of a gasification agent, and regulating and controlling reaction parameters as follows: the reaction pressure is normal pressure (or micro-positive pressure), the reaction temperature is 700-900 ℃, and the initial reaction space velocity is 1-100L/(g)Semi-cokeH), carrying out constant-temperature reaction for 0.5-3 h in a fixed bed or fluidized bed reactor.
Step four, collecting reaction products: collecting the pyrolysis gas generated in the second step, namely high-calorific-value fuel gas; collecting the biomass oil produced in the second step; collecting the gaseous product produced in the third step, and supplementing the gaseous product for being used as a part of the pyrolysis atmosphere; and (4) collecting the solid product after the reaction in the step three, and using the solid product as an electrode material of the super capacitor.
The main components of the metal salt reagent are any one or more of nickel nitrate, ferric nitrate, cobalt nitrate and manganese nitrate.
The dosage of the biomass particles and the metal salt reagent is calculated according to the mass ratio of the biomass particles to the metal simple substance in the metal salt reagent, and the range is (10-200): 1.
The solution prepared in advance in the second step refers to an organic matter-water solution formed by mixing any one or more of methanol, ethanol, isopropanol, acetone, cyclohexanone, diethyl ether and propylene oxide with water, wherein the volume ratio of water to organic matter is (1-100) to 1.
The pyrolysis atmosphere refers to any one or more of hydrogen, synthesis gas, pyrolysis gas produced in the second step and methane.
The gasifying agent refers to any one or more of water vapor, carbon dioxide, air and oxygen.
Example 1
Step one, drying and crushing biomass raw materials: pine sawdust is used as a biomass raw material, pre-dried at the temperature of 100 ℃, and then crushed into small particles with the particle size of 100-150 mu m.
Step two, catalytic pyrolysis of biomass: the dried and crushed pine sawdust particles and a nickel nitrate reagent are weighed according to the mass ratio of 50:1 of the pine sawdust to the nickel simple substance, then are placed into a pre-prepared water-ethanol (the volume ratio of the pine sawdust to the nickel simple substance is 5:1) solution to be stirred and mixed, and then are dried at 100 ℃ and pyrolyzed for 30 minutes at 400 ℃ under the protection of hydrogen atmosphere, so that pyrolysis gas, biomass oil and pyrolysis semicoke loaded with nickel oxide are produced.
Step three, partial gasification reaction of pyrolysis semicoke: and (3) carrying out gasification reaction on the pyrolysis semicoke produced in the step two under the action of carbon dioxide, and regulating and controlling reaction parameters as follows: the reaction pressure is normal pressure, the reaction temperature is 750 ℃, and the initial reaction space velocity is 10L/(g)Semi-cokeH), a reaction is carried out in a fixed-bed reactor at constant temperature for 1 h.
Step four, collecting reaction products: the pyrolysis gas produced in the second step is high-calorific-value fuel gas (the main components are CO and H)2、CH4And CO2The high calorific value is as high as 7.21MJ/Nm3) (ii) a Collecting the biomass oil produced in the second step; collecting the gaseous products (mainly CO and unconverted CO) produced in the third step2) Supplementally used as part of the pyrolysis atmosphere. And (3) collecting the solid product after the reaction in the third step, namely the biomass charcoal-metal oxide composite material (the scanning electron microscope image of which is shown in fig. 1(a), and the scanning electron microscope image of the product obtained under the same condition without introducing nickel nitrate is shown in fig. 1(b)), and XPS (shown in fig. 2) shows that the NiO content of the surface of the composite material accounts for 56.5% of the total amount of the nickel metal on the surface.
When the biomass carbon-metal oxide composite material is used as an electrode material of a supercapacitor, a cyclic voltammetry curve of a traditional three-electrode test system (6mol/L KOH solution is used as an electrolyte, a platinum wire is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and an electrode prepared from the biomass carbon-metal oxide composite material is used as a working electrode) is shown in fig. 3(a) (wherein, obvious bulges are formed, and oxidation-reduction reactions of faradaic pseudo capacitance exist in the electrode material), and a constant current charging-discharging curve is shown in fig. 3 (b). When the current density is 1A/g, the capacitance value of the biomass charcoal-metal oxide composite material electrode can be calculated to be up to 234.0F/g, which is 1.91 times higher than that of the initial pyrolysis semicoke (80.4F/g), and 1.08 times higher than that of a biomass porous charcoal electrode prepared by not introducing nickel nitrate under the same condition (112.6F/g).
Example 2
Step one, drying and crushing biomass raw materials: corn straws are used as a biomass raw material, pre-dried at the temperature of 110 ℃, and then crushed into small particles with the particle size of 200-300 mu m.
Step two, catalytic pyrolysis of biomass: the dried and crushed pine sawdust particles and a nickel nitrate reagent are weighed according to the mass ratio of the pine sawdust to the nickel simple substance of 10:1 respectively, then are placed into a water-acetone (the volume ratio of the pine sawdust to the nickel simple substance of 10:1) solution prepared in advance to be stirred and mixed, and then are dried at 110 ℃ in sequence and pyrolyzed for 100 minutes at 350 ℃ under the protection of methane atmosphere, so that pyrolysis gas, biomass oil and pyrolysis semicoke loaded with nickel oxide can be produced.
Step three, partial gasification reaction of pyrolysis semicoke: and (3) carrying out gasification reaction on the pyrolysis semicoke produced in the step two under the action of water vapor, and regulating and controlling reaction parameters as follows: the reaction pressure is micro-positive pressure (about 2-3 kPa), the reaction temperature is 700 ℃, and the initial reaction space velocity is 100L/(g)Semi-cokeH), a thermostatical reaction of 0.5h is carried out in a fixed-bed reactor.
Step four, collecting reaction products: the pyrolysis gas produced in the second step is the fuel gas with high calorific value (the main component is H)2、CO、CO2And CH4The high calorific value is as high as 5.62MJ/Nm3) (ii) a Collecting the biomass produced in the second stepAn oil; collecting the gaseous product (mainly H) produced in the third step2CO and CO2) And may be used as part of the pyrolysis atmosphere. And (3) collecting the solid product obtained after the reaction in the third step, namely the biomass carbon-metal oxide composite material, wherein XPS (X-ray diffraction) detection shows that the NiO content of the surface of the composite material accounts for 40.2% of the total amount of the nickel metal on the surface.
When the biomass charcoal-metal oxide composite material is used as an electrode material of a super capacitor, the three-electrode test system in example 1 is adopted to detect and find that: when the current density is 1A/g, the capacitance value of the electrode is as high as 174.3F/g, which is 1.17 times higher than that of the initial pyrolysis semicoke, and the capacitance value of the electrode is 51.3% higher than that of a biomass porous carbon electrode prepared under the same condition without introducing nickel nitrate.
Example 3
Step one, replacing the pine sawdust in the embodiment 1 with peanut shells.
Step two, catalytic pyrolysis of biomass: the dried and crushed peanut shells and the nickel nitrate reagent are weighed according to the mass ratio of the peanut shells to the nickel simple substance of 200:1 respectively, then are placed into a prepared water-ether-propylene oxide (the volume ratio of the three is 5:1:1) solution to be stirred and mixed, and then are dried at 110 ℃ in sequence and pyrolyzed for 50 minutes at 550 ℃ under the protection of methane atmosphere, so that pyrolysis gas, biomass oil and pyrolysis semicoke loaded with nickel oxide can be produced.
Step three, partial gasification reaction of pyrolysis semicoke: and (3) carrying out gasification reaction on the pyrolysis semicoke produced in the second step under the action of air and carbon dioxide (the volume ratio of the air to the carbon dioxide is 1:9), and regulating and controlling reaction parameters as follows: the reaction pressure is normal pressure, the reaction temperature is 900 ℃ respectively, and the initial reaction space velocity is 1L/(g)Semi-cokeH), a thermostatical reaction of 0.5h is carried out in a fixed-bed reactor.
Step four, collecting reaction products: the pyrolysis gas produced in the second step is the fuel gas with high calorific value (the main component is H)2、CO、CO2And CH4The high calorific value is as high as 6.25MJ/Nm3) (ii) a Collecting the biomass oil produced in the second step; collecting the gaseous products (mainly CO and CO) produced in the third step2And nitrogen) are also providedMay be used in addition as part of the pyrolysis atmosphere. And (3) collecting the solid product obtained after the reaction in the third step, namely the biomass carbon-metal oxide composite material, wherein XPS (X-ray diffraction) detection shows that the NiO content of the surface of the composite material accounts for 70.8% of the total amount of the nickel metal on the surface.
When the biomass charcoal-metal oxide composite material is used as an electrode material of a super capacitor, the three-electrode test system in example 1 is adopted to detect and find that: when the current density is 1A/g, the capacitance value of the electrode is as high as 165.7F/g, which is 1.23 times higher than that of the initial pyrolysis semicoke, and the capacitance value of the electrode is 34.6% higher than that of a biomass porous carbon electrode prepared under the same condition without introducing nickel nitrate.
Example 4
Step one, replacing the pine sawdust in the example 1 with walnut shells.
Step two, catalytic pyrolysis of biomass: weighing the dried and crushed walnut shells and a nickel nitrate reagent according to the mass ratio of the walnut shells to the nickel simple substance of 100:1 respectively, placing the walnut shells and the nickel nitrate reagent into a prepared water-methanol-cyclohexanone (the volume ratio of the walnut shells to the nickel simple substance of 5:1:1) solution, stirring and mixing, and then drying and synthesizing gas (H) at 110 ℃ in sequence2And CO in a volume ratio of 1:1) for 60 minutes at 450 ℃, and pyrolysis gas, biomass oil and pyrolysis semicoke loaded with nickel oxide can be produced.
Step three, partial gasification reaction of pyrolysis semicoke: and (3) carrying out gasification reaction on the pyrolysis semicoke produced in the second step under the action of water vapor and carbon dioxide (the volume ratio of the water vapor to the carbon dioxide is 1:1), and regulating and controlling reaction parameters as follows: the reaction pressure is normal pressure, the reaction temperature is 800 ℃ respectively, and the initial reaction space velocity is 20L/(g)Semi-cokeH), a thermostatical reaction is carried out in a fixed-bed reactor for 3 h.
Step four, collecting reaction products: the pyrolysis gas produced in the second step is the fuel gas with high calorific value (the high calorific value is as high as 5.67 MJ/Nm)3) (ii) a Collecting the biomass oil produced in the second step; collecting the gaseous products (mainly CO and CO) produced in the third step2And H2) It may also be used as a supplement to the pyrolysis atmosphere. Collecting the solid product after the reaction in the third step, namely the biomass charcoal-metal oxide compositeAnd XPS detection shows that the NiO content of the surface of the composite material accounts for 44.7 percent of the total amount of the nickel metal on the surface.
When this biomass charcoal-metal oxide composite material is used as an electrode material of a supercapacitor, it was detected in the three-electrode test system in example 1 that: when the current density is 1A/g, the capacitance value of the electrode is as high as 145.9F/g, which is 1.15 times higher than that of the initial pyrolysis semicoke, and the capacitance value of the electrode is 32.8% higher than that of a biomass porous carbon electrode prepared under the same condition without introducing nickel nitrate.
Example 5
The nickel nitrate in the second step of the example 1 is replaced by ferric nitrate, and the prepared water-methanol-cyclohexanone (the volume ratio of the three is 5:1:1) solution is replaced by water-ethanol-isopropanol (the volume ratio of the three is 5:3:2) solution, so that the co-production of high calorific value fuel gas (the high calorific value is up to 6.43 MJ/Nm) can be achieved3) The biomass oil and the high-performance biomass charcoal-metal oxide composite electrode material (the capacitance value of the electrode material is up to 199.7F/g under the current density of 1A/g).
Example 6
The nickel nitrate in the second step of the example 2 is replaced by cobalt nitrate, and the gasifying agent (namely water vapor) in the third step is replaced by water vapor and oxygen (the volume ratio of the water vapor to the oxygen is 20:1), so that the co-production of high-calorific-value fuel gas (the high calorific value is as high as 6.58 MJ/Nm) can be achieved3) The biomass oil and the high-performance biomass charcoal-metal oxide composite electrode material (the capacitance value of the electrode material is up to 212.4F/g under the current density of 1A/g).
Example 7
The nickel nitrate in the second step of the example 1 is replaced by the manganese nitrate, and the co-production of fuel gas with high calorific value (the high calorific value is as high as 6.12 MJ/Nm) can be achieved3) The biomass oil and the high-performance biomass charcoal-metal oxide composite electrode material (the capacitance value of the electrode material is up to 231.8F/g under the current density of 1A/g).
Example 8
The nickel nitrate in step two of example 3 was replaced with a mixture of nickel nitrate and manganese nitrate such that the initial mass ratio of biomass particles to Ni was 200:1 and biomass was bio-generatedWhen the initial mass ratio of the mass particles to Mn is 10:1, the co-production of fuel gas with high calorific value (the high calorific value is as high as 6.73 MJ/Nm)3) The biomass oil and the high-performance biomass charcoal-metal oxide composite electrode material (the capacitance value of the material is up to 261.3F/g under the current density of 1A/g). .
Example 9
The nickel nitrate in the second step of example 3 was replaced by a mixture of ferric nitrate and manganese nitrate such that when the initial mass ratio of biomass particles to Fe was 200:1 and the initial mass ratio of biomass particles to Mn was 10:1, the co-production of high calorific value fuel gas (high calorific value up to 6.24 MJ/Nm) was also achieved3) The biomass oil and the high-performance biomass charcoal-metal oxide composite electrode material (the capacitance value of the electrode material is as high as 305.1F/g under the current density of 1A/g).
Example 10
The nickel nitrate in the second step of example 3 is replaced by a mixture of ferric nitrate and nickel nitrate, so that when the initial mass ratio of biomass particles to Ni is 200:1 and the initial mass ratio of biomass particles to Fe is 10:1, the co-production of fuel gas with high calorific value (the high calorific value is as high as 6.97 MJ/Nm) can be achieved3) The biomass oil and the high-performance biomass charcoal-metal oxide composite electrode material (the capacitance value of the electrode material is up to 218.3F/g under the current density of 1A/g).

Claims (9)

1. A preparation method of a biomass charcoal-metal oxide composite electrode material is characterized by comprising the following steps:
drying a biomass raw material, and then crushing the biomass raw material into biomass particles;
adding the biomass particles and a metal salt reagent into an organic matter-water solution, uniformly mixing, drying, and then pyrolyzing at 350-550 ℃ for 30-100 minutes under the protection of pyrolysis atmosphere to produce pyrolysis gas, biomass oil and metal-loaded pyrolysis semicoke;
and step three, carrying out gasification reaction on the metal-loaded pyrolysis semicoke produced in the step two under the action of a gasification agent to obtain the biomass carbon-metal oxide composite electrode material.
2. The preparation method of the biomass charcoal-metal oxide composite electrode material according to claim 1, wherein in the first step and the second step, the drying temperature is 100-110 ℃, and the particle size of the biomass particles is 100-300 μm.
3. The preparation method of the biomass charcoal-metal oxide composite electrode material according to claim 1, wherein in the first step, the biomass raw material is pine wood chips, corn stalks, peanut shells or walnut shells.
4. The method for preparing the biomass charcoal-metal oxide composite electrode material according to claim 1, wherein in the second step, the metal salt reagent is any one or more of nickel nitrate, ferric nitrate, cobalt nitrate and manganese nitrate.
5. The method for preparing the biomass charcoal-metal oxide composite electrode material according to claim 1, wherein in the second step, the organic matter-water solution is a mixture of water and any one or more of methanol, ethanol, isopropanol, acetone, cyclohexanone, diethyl ether and propylene oxide.
6. The preparation method of the biomass charcoal-metal oxide composite electrode material as claimed in claim 1, wherein in the second step, the usage amount of the biomass particles and the metal salt reagent is calculated according to the mass ratio of the biomass particles to the metal simple substance in the metal salt reagent being (10-200): 1.
7. The method for preparing the biomass charcoal-metal oxide composite electrode material according to claim 1, wherein in the second step, the pyrolysis atmosphere is any one or more of hydrogen, synthesis gas, pyrolysis gas and methane.
8. The method for preparing the biomass charcoal-metal oxide composite electrode material according to claim 1, wherein in the third step, the gasifying agent is any one or more of water vapor, carbon dioxide, air and oxygen.
9. The preparation method of the biomass charcoal-metal oxide composite electrode material according to claim 1, wherein in the third step, the gasification reaction process is as follows: under normal pressure or micro-positive pressure, at a temperature of 700-900 ℃ and an initial reaction space velocity of 1-100L/(g)Semi-cokeH), carrying out constant-temperature reaction for 0.5-3 h in a fixed bed or fluidized bed reactor.
CN202110561067.2A 2021-05-21 2021-05-21 Preparation method of biomass charcoal-metal oxide composite electrode material Pending CN113249142A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110561067.2A CN113249142A (en) 2021-05-21 2021-05-21 Preparation method of biomass charcoal-metal oxide composite electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110561067.2A CN113249142A (en) 2021-05-21 2021-05-21 Preparation method of biomass charcoal-metal oxide composite electrode material

Publications (1)

Publication Number Publication Date
CN113249142A true CN113249142A (en) 2021-08-13

Family

ID=77183778

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110561067.2A Pending CN113249142A (en) 2021-05-21 2021-05-21 Preparation method of biomass charcoal-metal oxide composite electrode material

Country Status (1)

Country Link
CN (1) CN113249142A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008055591A2 (en) * 2006-11-09 2008-05-15 Paul Scherrer Institut Method and plant for converting solid biomass into electricity
EP2501788A1 (en) * 2009-11-18 2012-09-26 G4 Insights Inc. Sorption enhanced methanation of biomass
CN106531476A (en) * 2016-12-29 2017-03-22 湖北文理学院 Preparation method of metal oxide/ carbon composite material
CN107649134A (en) * 2017-11-13 2018-02-02 西北大学 A kind of method for preparing porous charcoal metal supported catalyst using coal or gasification of biomass

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008055591A2 (en) * 2006-11-09 2008-05-15 Paul Scherrer Institut Method and plant for converting solid biomass into electricity
EP2501788A1 (en) * 2009-11-18 2012-09-26 G4 Insights Inc. Sorption enhanced methanation of biomass
CN106531476A (en) * 2016-12-29 2017-03-22 湖北文理学院 Preparation method of metal oxide/ carbon composite material
CN107649134A (en) * 2017-11-13 2018-02-02 西北大学 A kind of method for preparing porous charcoal metal supported catalyst using coal or gasification of biomass

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MA, XF ET AL.: "Modification of porous starch for the adsorption of heavy metal ions from aqueous solution", 《FOOD CHEMISTRY》 *
张永杰等: "《钢铁低碳高能效共性难题技术研发与应用》", 31 August 2019 *

Similar Documents

Publication Publication Date Title
Wang et al. Hydrogen-rich syngas production from biomass pyrolysis and catalytic reforming using biochar-based catalysts
Ji et al. Review and comparison of various hydrogen production methods based on costs and life cycle impact assessment indicators
You et al. A critical review on sustainable biochar system through gasification: Energy and environmental applications
Peng et al. Hydrogen and syngas production by catalytic biomass gasification
Kırtay Recent advances in production of hydrogen from biomass
Nath et al. Hydrogen from biomass
Ali et al. Biofuels production from weed biomass using nanocatalyst technology
Nguyen-Thi et al. Recent advances in hydrogen production from biomass waste with a focus on pyrolysis and gasification
Xiong et al. Research progress on pyrolysis of nitrogen-containing biomass for fuels, materials, and chemicals production
CN102977927A (en) Apparatus for preparing synthesis gas based on dual fluidized bed biomass gasification and preparation method thereof
Kaur et al. Thermochemical route for biohydrogen production
Pocha et al. Thermochemical conversion of different biomass feedstocks into hydrogen for power plant electricity generation
CN111363572B (en) Method for co-producing gas-liquid fuel, chemicals and carbon materials by catalytic pyrolysis of biomass
US20210140054A1 (en) Methods and systems for the generation of high purity hydrogen with co2 capture from biomass and biogenic wastes
CN108889300A (en) A kind of preparation method and applications of novel hydro-thermal charcoal carried nanometer bi-metal catalyst
CN106966359A (en) The method that the catalysis of transition metal iridium prepares hydrogen from the hydrolyzate of biomass and house refuse
CN100560202C (en) A kind of modification dolomite and its production and application
Bhakta et al. The emerging role of biochar in the carbon materials family for hydrogen production
CN112063394A (en) Method for producing hydrogen-rich synthesis gas by gasifying waste biomass
Lu et al. Parametric study of catalytic co-gasification of cotton stalk and aqueous phase from wheat straw using hydrothermal carbonation
Wang et al. Catalytic gasification of rice hull by dielectric barrier discharge non-thermal plasma over potassium catalyst
CN100363249C (en) Method of preparing hydrogen gas by catalytic gasifying hydrolysis residue of cellulose castoff
Goren et al. Comparative environmental sustainability assessment of biohydrogen production methods
Liu et al. A green route for hydrogen production from alkaline thermal treatment (ATT) of biomass with carbon storage
CN106590705A (en) Method for secondarily reforming tar by utilizing in-situ composite semicoke made from high alkaline coal and biomass

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20220630

Address after: No.166, Shenzhou seventh Road, Xi'an space base, Shaanxi 710100

Applicant after: SHAANXI COAL AND CHEMICAL TECHNOLOGY INSTITUTE Co.,Ltd.

Applicant after: Northwestern University

Address before: No. 229, Taibai North Road, Xi'an, Shaanxi 710127

Applicant before: NORTHWEST University

TA01 Transfer of patent application right