CN114107405A - Method for preparing lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst - Google Patents
Method for preparing lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst Download PDFInfo
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
Abstract
The invention discloses a method for preparing a lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst. In particular to two processes of acid production and charcoal production of lignocellulose biomass. Firstly, the raw material adopts a hydrothermal pretreatment mode, then the pretreated raw material is mixed with the inoculum, and acid production is carried out after the pH value of an acid production system is directionally regulated to 10-11. The solid phase product of the acid production process is used for directionally producing carbon, the internal structure of the biomass is opened under the action of microorganisms, and meanwhile, the nitrogen-rich raw material microbial thallus is introduced, nitrogen is introduced into a carbon skeleton through high-temperature pyrolysis in an inert atmosphere to form abundant nitrogen-containing functional groups, so that the nitrogen-rich pyrolysis and conversion of the lignocellulose biomass are realized, and finally, the functional high-nitrogen-containing porous carbon material with abundant nitrogen-containing functional groups is formed.
Description
Technical Field
The invention belongs to the technical field of biomass utilization, and particularly relates to a method for preparing a lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst.
Background
Lignocellulose biomass is the most abundant biomass resource on the earth, comprises wood (such as eucalyptus, beech, poplar and the like) and agricultural and forestry waste (such as corn stalks, wheat stalks, sorghum stalks and the like), and has the characteristics of wide source, universality, easiness in taking and the like. Lignocellulosic biomass is mainly composed of cellulose, hemicellulose, lignin and the like, which are strongly engaged by covalent bonds or non-covalent bonds, so that plants have a stable three-dimensional pore structure. The unique pore structure provides convenience for constructing a complex hierarchical pore structure carbon material, but the strong crosslinking effect makes the appearance and the structure of a product difficult to be accurately regulated and controlled.
The doping of hetero atoms (N, P, S, B, F and the like) is an important strategy for improving the oxygen reduction performance of the carbon material, and particularly, the introduction of a nitrogen-containing functional group has an obvious effect on improving the electrochemical quality of the carbon material. The nitrogen atoms are similar in size to the carbon atoms and can therefore be readily substituted for the carbon atoms in the carbon nanomaterial. On the other hand, N-doped atoms have a higher electron affinity compared to C atoms, which makes it easy for the N-doped atoms to change the atomic structure and the electron arrangement in the carbon material, thereby resulting in delocalization of charges, variation in spin density, and an increase in density of states closer to the fermi level in the carbon nanomaterial. The optimization further enables the carbon material to have n-type conductivity, the metal performance is improved, the electron transfer rate is improved, and more active sites are provided for reactants. The nitrogen-rich bound form allows the carbon-based material to exhibit different characteristics.
Existing patents on the preparation of biochar electrode materials have focused more on the efficient conversion of nitrogen-rich biomass, such as (CN104241662A), primarily on the regulation of the pyrolysis process of nitrogen-rich biomass. At present, no relevant report of preparing the high-nitrogen-content porous carbon material through biological process regulation is found. Therefore, the development of a simple, cheap and efficient biomass-based nitrogen-doped hierarchical structure porous carbon material has great significance.
Disclosure of Invention
The first purpose of the invention is to provide a method for preparing a lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst.
The invention realizes nitrogen-rich pyrolysis and structure regulation of common lignocellulose biomass through biological process regulation. Through surface modification and structure adjustment, heterogeneous doping, defect sites and adjustment of nano-scale pores, holes and channels are formed in the porous carbon material, so that the activity, selectivity and stability of the catalyst can be remarkably improved, and the specific energy density of the battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst comprises the following steps:
s1: pretreating lignocellulose biomass in a hydrothermal reaction kettle;
s2: transferring the material pretreated in the step S1 to an acid-producing reactor, adding an inoculum, adjusting the pH, performing solid-liquid separation after running for a period of time, wherein the collected liquid part is rich in volatile organic acid;
s3: drying the solid part collected in the step S2, and then carrying out nitrogen-rich pyrolysis reaction in an inert atmosphere to obtain nitrogen-doped biochar;
s4: and (4) carrying out acid washing on the biochar obtained in the step (S3), then washing with excessive deionized water until filtrate is neutral, and drying to obtain the functional high nitrogen-containing porous carbon material rich in nitrogen functional groups, namely the nitrogen-rich carbon-based oxygen reduction catalyst.
Further, the conditions of the preprocessing in the step S1 are: the solvent is water, the temperature is 160-200 ℃, the time is 2-6 h, and the solid-to-liquid ratio is 1: 15-20.
Further, the acid production reactor in the step S2 adopts a sequencing batch feeding mode, and the material retention time is 4-6 d; the operation pH value of the acid production reactor is adjusted to 10-11, the operation temperature is 35-55 ℃, and the operation time is 4-10 d.
Further, the solid-liquid separation in step S2 is performed by a high-speed centrifuge.
Further, the temperature of the nitrogen-rich pyrolysis reaction in the step S3 is 600-1200 ℃, and the heating rate is 1-20 ℃/min.
Furthermore, the regulation and control mode of the nitrogen-rich pyrolysis reaction process in the step S3 comprises activation regulation and control, and the regulation and control activating agent is selected from KOH and ZnCl2、K2CO3、HPO4At least one of basic carbonate and ionic liquid.
Further, the lignocellulose biomass is selected from at least one of straw, pennisetum, paper mulberry and beech.
The principle of the invention is as follows: firstly, the hemicellulose and part of cellulose in the lignocellulose biomass components are directionally degraded in the anaerobic fermentation process, the loose structure is realized, the conversion rate of the fibers of the lignocellulose biomass raw materials in the anaerobic process is not high, about 20-60% of the fibers cannot be utilized, and the unconverted cellulose and lignin have loose structures and smooth pore passages, so that the full infiltration of an activating agent is facilitated, and the abundance of the pore passage structures of carbon products is improved. In addition, the loose pore channels provide convenient conditions for the uniform attachment of microbial thalli, so that the microbial thalli of the nitrogen-rich raw material can be uniformly attached to the raw material in the fermentation process, and a large amount of residual microbial thalli can be used as the nitrogen-rich raw material to supplement a nitrogen source for a biomass body so as to realize nitrogen enrichment, thereby providing necessary conditions for the nitrogen-rich pyrolysis conversion of the microbial thalli; secondly, in the nitrogen-rich pyrolysis process, part of carbon atoms generate gaseous and liquid products, and meanwhile, the nitrogen atoms are doped in the carbon atom combination process to form rich active nitrogen-containing functional groups (such as pyridine-N, pyrrole-N, graphite-N and the like), and finally, the functional high-nitrogen-containing porous carbon material with rich active nitrogen-containing functional groups is formed.
The second purpose of the invention is to provide a high nitrogen-containing porous carbon material prepared by the method for preparing the lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst.
In the high nitrogen-containing porous carbon material, the existence form of nitrogen comprises pyridine-N, pyrrole N or graphite-N.
The functional high-nitrogen-content porous carbon material obtained by the method has a developed pore structure and rich active nitrogen-containing functional groups, and has wide application prospects, such as application as an oxygen reduction catalyst, an electrode material and the like.
Therefore, the third purpose of the invention is to provide the application of the high nitrogen-containing porous carbon material as an oxygen reduction catalyst or an electrode material.
The invention has the technical effects that:
1. in the method, the lignocellulose biomass is used for preparing the high-nitrogen porous carbon material, so that a high-valued utilization method can be provided for biomass waste.
2. In the method, lignocellulose biomass is used for preparing the high-nitrogen porous carbon material, structure depolymerization and nitrogen enrichment are realized through anaerobic fermentation, and the porous carbon material with the hierarchical structure rich in nitrogen functional groups (such as pyridine-N, pyrrole-N and graphite-N) is obtained through further nitrogen-rich pyrolysis.
3. In the method, the structure depolymerization and nitrogen enrichment of the lignocellulose biomass can be realized by adjusting the anaerobic fermentation process, the operation is simple, the control is easy, the cost is low, the high-nitrogen-content porous carbon material can be obtained by one-step nitrogen-rich pyrolysis, and the specific surface area of the high-nitrogen-content porous carbon material reaches 1057.9m2The nitrogen content reaches 8.32 percent; and liquid oil and pyrolysis gas byproducts generated by nitrogen-rich pyrolysis can be further developed and utilized, such as liquid oil separation and purification to prepare high value-added compounds.
4. The functional high-nitrogen-content porous carbon material obtained by the method has a developed pore structure and rich active nitrogen-containing functional groups, and the nitrogen-containing functional groups have good dispersibility and wide application prospect in the field of electrocatalysis.
5. The volatile organic acid prepared by the method can be used as a chemical raw material, and the obtained high-nitrogen-content porous carbon material can be applied to electrocatalytic oxygen reduction reaction. For example, lactic acid can be used for producing polylactic acid, and the high-nitrogen-content porous carbon material can be used as a preparation material of air cathode fuel cells such as microbial fuel cells and hydrogen-oxygen fuel cells.
Drawings
FIG. 1 is SEM images of broussonetia papyrifera before and after fermentation in example 1 of the invention. The broussonetia papyrifera residue in the figure is fermented broussonetia papyrifera.
FIG. 2 is an XPS spectrum of N1s of the high nitrogen content porous carbon material prepared in example 1 of the present invention. In the figure, Pyridine N is Pyridine N, Pyrrolic N is pyrrole N, and graphite N is graphite-N.
FIG. 3 is a diagram showing the electrocatalytic oxygen reduction reaction of the directly pyrolyzed porous carbon material (g @ C) obtained by fermenting paper mulberry in example 1 of the present invention, and the pyrolyzed porous carbon material (gz @ C) obtained by fermenting paper mulberry.
Detailed Description
In order to make the above objects of the present invention more comprehensible, embodiments of the present invention are described in detail below with reference to specific examples, but the scope of the present invention is not limited to the following examples.
Example 1
A method for jointly producing acid and a high-nitrogen-content porous carbon material by using a paper mulberry comprises the following steps:
s1: crushing paper mulberry, mixing the paper mulberry with water according to the solid-to-liquid ratio of 1:20, and pretreating for 6 hours in a hydrothermal reaction kettle at 200 ℃.
S2: transferring the pretreated material in the step S1 to an acid production reactor in a sequencing batch feeding manner, keeping the material for 5 days, and adding livestock manure inoculum (VS)Substrate：VSInoculum3: 1) adjusting pH to 11, operating at 55 ℃ for 10 days, then separating solid and liquid by adopting a high-speed centrifuge, wherein the collected liquid part is rich in volatile organic acid, and the content of the organic acid can reach 10 g/L.
S3: the solid portion collected in step S2 was dried in an oven at 105 ℃ to a constant weight to obtain a feedstock to be pyrolyzed.
S4: the raw material to be pyrolyzed obtained in step S3 is mixed with K2CO3Fully mixing the components according to the mass ratio of 1:1, adding 10mL of deionized water, magnetically stirring the mixture for 8 hours at a constant temperature, putting the fully mixed suspension into a vacuum drying oven, and drying the suspension at 60 ℃ for later use.
S5: and (3) putting the dried solid of S4 into a vacuum tube furnace, carrying out pyrolysis reaction at 900 ℃ in a nitrogen atmosphere, annealing for 2h at the heating rate of 5 ℃/min, and thus obtaining the nitrogen-doped biochar.
S6: and (4) carrying out acid washing on the nitrogen-doped biochar obtained in the step (S5), wherein the concentration of a hydrochloric acid solution is 1mol/L, then washing with excessive deionized water until filtrate is neutral, carrying out suction filtration and drying to obtain the functional high nitrogen-containing porous carbon material rich in nitrogen functional groups, namely the nitrogen-rich carbon-based oxygen reduction catalyst.
After the obtained high-nitrogen-content porous carbon material is characterized, the result shows that the obtained material has a developed pore structure and the surface area reaches 1057.9m2The nitrogen content reaches 8.32 percent, and the nitrogen-containing functional group is rich (pyridine-N, pyrrole-N and graphite-N).
The nitrogen content before and after fermentation of paper mulberry was determined and the results are shown in table 1. As can be seen from Table 1, nitrogen element is significantly increased after fermentation of paper mulberry, which is 26.88% higher than that before fermentation.
TABLE 1
FIG. 1 is SEM pictures of broussonetia papyrifera before and after fermentation in example 1 of the present invention. As can be seen from the SEM image, the structure of the paper mulberry is obviously changed after the paper mulberry is subjected to anaerobic fermentation, the original compact structure is destroyed, and the surface of the paper mulberry is rougher, so that the attachment of the nitrogen-rich raw material microbial thalli is facilitated.
FIG. 2 is an XPS spectrum of N1s of the high nitrogen content porous carbon material prepared in example 1 of the present invention. The experimental result shows that the high nitrogen-containing porous carbon material has a developed pore structure and the surface area reaches 1057.9m2The nitrogen content of the material reaches 8.32 percent.
FIG. 3 shows the oxygen reduction performance of a porous carbon material g @ C obtained by direct pyrolysis of paper mulberry (without fermentation treatment) and a porous carbon material gz @ C obtained by pyrolysis after fermentation of paper mulberry. As can be seen from fig. 3, the initial potential of the catalytic oxygen reduction reaction of the porous carbon material prepared by pyrolysis of the fermentation-treated broussonetia papyrifera is significantly shifted forward, which indicates that the electrocatalytic oxygen reduction performance of the electrode carbon material obtained by pyrolysis is significantly improved by the raw material after fermentation treatment.
The above results show that: the high-nitrogen-content porous carbon material prepared by the method can be applied to electrocatalytic oxygen reduction reaction. For example, the catalyst is used for air cathode fuel cells such as microbial fuel cells and hydrogen-oxygen fuel cells, and catalyzes oxygen reduction reaction.
Example 2
A method for jointly producing acid and a high-nitrogen-content porous carbon material by utilizing hybrid pennisetum comprises the following steps:
s1: crushing the hybrid pennisetum alopecuroides, mixing the crushed hybrid pennisetum alopecuroides with water according to the solid-to-liquid ratio of 1:15, and pretreating the crushed hybrid pennisetum alopecuroides for 4 hours at 180 ℃ in a hydrothermal reaction kettle.
S2: transferring the pretreated material in the step S1 to an acid production reactor in a sequencing batch feeding manner, keeping the material for 5 days, and adding livestock manure inoculum (VS)Substrate：VSInoculum3: 1) adjusting pH to 10, operating at 35 deg.C for 4d, and performing solid-liquid separation by high-speed centrifuge, wherein the collected liquid part is rich in volatile organic acid with organic acid content of 5 g/L.
S3: the solid portion collected in step S2 was dried in an oven at 105 ℃ to a constant weight to obtain a feedstock to be pyrolyzed.
S4: the raw material to be pyrolyzed obtained in step S3 is mixed with ZnCl2Fully mixing the components according to the mass ratio of 1:1, adding 10mL of deionized water, magnetically stirring the mixture for 8 hours at a constant temperature, putting the fully mixed suspension into a vacuum drying oven, and drying the suspension at 60 ℃ for later use.
S5: and (3) putting the dried solid of S4 into a vacuum tube furnace, carrying out pyrolysis reaction at 1200 ℃ in a nitrogen atmosphere, annealing for 2h at the heating rate of 20 ℃/min, and thus obtaining the nitrogen-doped biochar.
S6: and (4) carrying out acid washing on the nitrogen-doped biochar obtained in the step (S5), wherein the concentration of a hydrochloric acid solution is 1mol/L, then washing with excessive deionized water until filtrate is neutral, carrying out suction filtration and drying to obtain the functional high nitrogen-containing porous carbon material rich in nitrogen functional groups, namely the nitrogen-rich carbon-based oxygen reduction catalyst.
Through detection, the surface area of the high-nitrogen-content porous carbon material prepared in the embodiment 2 of the invention reaches 1032.5m2The nitrogen content is 5.23 percent per gram.
Example 3
A method for jointly producing acid and a high-nitrogen-content porous carbon material by using crop straws comprises the following steps:
s1: crushing straws, mixing the straws with water according to the solid-to-liquid ratio of 1:20, and pretreating for 6 hours in a hydrothermal reaction kettle at 200 ℃.
S2: transferring the pretreated material in the step S1 to an acid production reactor in a sequencing batch feeding manner, keeping the material for 5 days, and adding livestock manure inoculum (VS)Substrate：VSInoculum3: 1) adjusting pH to 10, operating at 35 deg.C for 6d, and performing solid-liquid separation by high-speed centrifuge, wherein the collected liquid part is rich in volatile organic acid with organic acid content of 6 g/L.
S3: the solid portion collected in step S2 was dried in an oven at 105 ℃ to a constant weight to obtain a feedstock to be pyrolyzed.
S4: the raw material to be pyrolyzed obtained in step S3 is mixed with K2CO3According to the qualityFully mixing the components in a weight ratio of 1:1, adding 10mL of deionized water, magnetically stirring the mixture for 8 hours at a constant temperature, putting the fully mixed suspension into a vacuum drying oven, and drying the suspension at 60 ℃ for later use.
S5: and (3) putting the dried solid of S4 into a vacuum tube furnace, carrying out pyrolysis reaction at 600 ℃ in a nitrogen atmosphere, annealing for 2h at the heating rate of 1 ℃/min, and thus obtaining the nitrogen-doped biochar.
S6: and (4) carrying out acid washing on the nitrogen-doped biochar obtained in the step (S5), wherein the concentration of a hydrochloric acid solution is 1mol/L, then washing with excessive deionized water until filtrate is neutral, carrying out suction filtration and drying to obtain the functional high nitrogen-containing porous carbon material rich in nitrogen functional groups, namely the nitrogen-rich carbon-based oxygen reduction catalyst.
Through detection, the surface area of the high-nitrogen-content porous carbon material prepared in the embodiment 3 of the invention reaches 1135.2m2The nitrogen content is 3.98 percent per gram.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A method for preparing a lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst is characterized by comprising the following steps:
s1: pretreating lignocellulose biomass in a hydrothermal reaction kettle;
s2: transferring the material pretreated in the step S1 to an acid-producing reactor, adding an inoculum, adjusting the pH, performing solid-liquid separation after running for a period of time, wherein the collected liquid part is rich in volatile organic acid;
s3: drying the solid part collected in the step S2, and then carrying out nitrogen-rich pyrolysis reaction in an inert atmosphere to obtain nitrogen-doped biochar;
s4: and (4) carrying out acid washing on the biochar obtained in the step (S3), then washing with excessive deionized water until filtrate is neutral, and drying to obtain the functional high nitrogen-containing porous carbon material rich in nitrogen functional groups, namely the nitrogen-rich carbon-based oxygen reduction catalyst.
2. The method of co-producing acid and nitrogen-rich char-based oxygen reduction catalyst from lignocellulosic biomass as claimed in claim 1, wherein the conditions of the pretreatment in step S1 are: the solvent is water, the temperature is 160-200 ℃, the time is 2-6 h, and the solid-to-liquid ratio is 1: 15-20.
3. The method for preparing the lignocellulose biomass co-produced acid and nitrogen-rich carbon-based oxygen reduction catalyst according to claim 1, wherein the acid production reactor in the step S2 adopts a sequencing batch feeding mode, and the material retention time is 4-6 days; the operation pH value of the acid production reactor is adjusted to 10-11, the operation temperature is 35-55 ℃, and the operation time is 4-10 d.
4. The method for coproducing acid and nitrogen-rich char-based oxygen reduction catalyst according to claim 1 or 3, wherein the solid-liquid separation in step S2 is performed by using a high-speed centrifuge.
5. The method for preparing the lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst as claimed in claim 1, wherein the temperature of the nitrogen-rich pyrolysis reaction in the step S3 is 600-1200 ℃, and the temperature rise rate is 1-20 ℃/min.
6. The method for coproducing acid and nitrogen-rich char-based oxygen reduction catalyst according to claim 1 or 5, wherein the manner of controlling the nitrogen-rich pyrolysis reaction process in the step S3 comprises activation control, and the control activator is selected from KOH and ZnCl2、K2CO3At least one of HPO4, alkali carbonate and ionic liquid.
7. The method of claim 1, wherein the lignocellulosic biomass is selected from at least one of straw, pennisetum, paper mulberry, and beech.
8. The high nitrogen-containing porous carbon material prepared by the method for preparing the lignocellulose biomass coproduction acid and nitrogen-rich carbon-based oxygen reduction catalyst according to claim 1.
9. The porous carbon material with high nitrogen content according to claim 8, wherein the nitrogen exists in a form of pyridine-N, pyrrole-N or graphite-N.
10. Use of the porous carbon material with high nitrogen content according to claim 8 or 9 as an oxygen reduction catalyst or an electrode material.
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