CN115784199A - Preparation method of potato straw biochar and application of potato straw biochar in anaerobic fermentation system - Google Patents
Preparation method of potato straw biochar and application of potato straw biochar in anaerobic fermentation system Download PDFInfo
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Abstract
The invention discloses a preparation method of potato straw biochar and application of the biochar in an anaerobic fermentation system, wherein the preparation method comprises the steps of cleaning, drying and crushing potato straws into particles with the particle size of 0.4-0.5mm, and placing the particles in a muffle furnace for anoxic carbonization; the carbonization temperature rise and temperature drop process is 250 ℃ for 5min; 300 ℃ for 10 min;400 ℃ for 15 min; 5min at 550 ℃; at 600 ℃,2h; at 550 ℃ for 25min;480 ℃,25 min;30 min at 380 ℃;30 min at 280 ℃; and finally, cooling to room temperature, taking out, and sealing for storage. The application method comprises the following steps: the method comprises the following steps of putting potato straw biochar, cow dung and tap water into a fermentation tank for fermentation, wherein the ratio of the air volume to the effective fermentation volume of the fermentation tank is 1. The method takes the agricultural waste straws and the livestock and poultry manure with lower value as the substrate to obtain the methane gas with higher value, and carries out effective resource treatment on the straws and the livestock and poultry manure, thereby improving the resource utilization efficiency of the agricultural waste materials.
Description
Technical Field
The invention relates to the technical field of biomass energy, in particular to a preparation method of potato straw biochar, and also relates to application of the potato straw biochar in an anaerobic fermentation system.
Background
The disposal of organic waste and the energy crisis are global issues. The agricultural waste mainly comprises agricultural straws and animal wastes. If the wastes are not properly treated, the wastes cause serious resource waste and environmental pollution. Since direct incineration of agricultural residues and livestock manure will create global greenhouse effect problems, emerging anaerobic digestion technologies play an important role in agricultural waste treatment and development of renewable energy sources, which can convert agricultural waste into biogas. The methane in the marsh gas is used as renewable energy and is expected to replace the traditional fossil fuel. However, the widespread use of anaerobic digestion techniques is limited by factors such as unstable operation, rapid acidification, low methane production, and the production of byproducts that are difficult to degrade. Therefore, it is urgent to improve the operation efficiency of the anaerobic digestion system and to improve the quality of biogas.
In recent years, some additives are applied to an anaerobic digestion system to improve digestion efficiency, such as graphene, carbon-based promoters, biological additives and the like, which can significantly improve anaerobic digestion performance. Although carbon-based promoters and enzyme additives have great potential in improving biogas productivity, both are not widely used due to the high cost. Biomass produces porous biochar in the thermochemical cracking of anaerobic environments, which is considered a promising additive in anaerobic digestion systems to enhance the operational stability of anaerobic digestion systems and increase methane production.
Biochar is widely concerned in waste treatment due to its unique characteristics, and its main advantages are porous structure, high specific surface area, special functional groups and high cation exchange capacity. In addition, biochar in the anaerobic digestion system can alter the composition of the microbial community, improve microbial metabolism, maintain stability of the anaerobic digestion process, and reduce inhibition of toxins. The biochar is added into an anaerobic digestion system to fix microorganisms, shorten the lag phase and promote the electron transfer of methanogens. And compared with a carbon-based promoter and graphene, the biochar is low in cost due to the fact that the biochar is derived from waste biomass, and therefore the optimal economy is displayed.
A large number of reports show that biochar produced by different raw materials has great difference in improving anaerobic digestion performance. Although crop straws are widely used for producing biochar, different crop straws exhibit different compositions and properties. Thus, biochar produced from different crop stalks can have different effects on the anaerobic digestion process. At present, researches on anaerobic digestion efficiency of common crop straws such as corn straws, rice straws and rice hull biochar are carried out, and related reports of potato straw biochar are not available, so that the potato straw biochar is not beneficial to full utilization of agricultural waste resources.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of potato straw biochar to improve the utilization rate of agricultural waste resources.
The invention also aims to provide the application of the potato straw biochar in an anaerobic fermentation system.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of potato straw biochar specifically comprises the following steps: cleaning potato straw, drying, pulverizing to particle size of 0.4-0.5mm, and carbonizing in muffle furnace under oxygen-deficient condition; the carbonization temperature rise and temperature drop process is 250 ℃ for 5min; 300. 10 min at the temperature; 400. 15 min at the temperature; 550. 5min at the temperature; 600. 2h deg.C; 550. 25min at the temperature; 480. 25min at the temperature; 380. 30min at the temperature; 280. 30min at the temperature; the heating and cooling rates are both 10 ℃/min; and finally, cooling to room temperature, taking out, and sealing for storage.
As the optimization of the technical scheme of the invention, the cleaning process is to cut the potato straws into small sections with the length of 2.5-3.5cm and wash the small sections with water.
Preferably, the drying process is that the potato straws cut into small sections are naturally dried in an outdoor drying and ventilating place and then put into an oven for drying.
The potato straw biochar can be used for an anaerobic fermentation system, and the specific operation method comprises the following steps: putting the potato straw biochar, the cow dung and the tap water into a fermentation tank for fermentation, wherein in a fermentation system, the adding amount of the potato straw biochar is 6-12 g/L, the weight of the cow dung solid accounts for 6-8% of the total fermentation system, and the tap water accounts for 90-95% of the total volume of the whole fermentation system; the total solid weight of the fermentation system is 8-10%, the fermentation temperature is 35-38 ℃, the ratio of the air volume of the fermentation tank to the effective fermentation volume is 1.
Preferably, the adding amount of the potato straw biochar is 10 g/L, the weight of the cow dung solid accounts for 6.2% of the total fermentation system, and tap water accounts for 95% of the total volume of the whole fermentation system; the total solid weight of the fermentation system is 8 percent, and the fermentation temperature is 38 ℃.
The invention has the beneficial effects that:
1. the preparation method of the potato straw biochar is simple to operate, and the surface area of the prepared potato straw biochar reaches 176.45 m 2 /g, rich in functional groups, e.g. aromatic, hydroxy, C-O, CH 2 、-CH 3 、CH n And a large amount of amino groups, the cation exchange capacity is large, the microorganism attachment capacity is good, the additive is applied to anaerobic fermentation to improve the efficiency of methanogenesis, compared with a control group without biochar, the efficiency of methanogenesis can be improved by 1.78 times, and archaea can be enriched in an anaerobic fermentation system.
2. The potato straw biochar is simple and convenient to add when being used in an anaerobic fermentation system, can be rapidly dispersed in the anaerobic fermentation system, is extremely easy to enrich microorganisms to form a biomembrane, and can remarkably improve the methane production efficiency of anaerobic fermentation and the methane content in methane.
3. According to the invention, cow dung in a dairy farm is used as a fermentation substrate, the potato straw biochar is added as an additive, methane is efficiently produced under a micro-oxygen environment of 1.
Drawings
FIG. 1 shows potato straw biochar under electron microscope scanning: (A) 450 ℃ charcoal; (B) 500 ℃ charcoal; (C) biochar at 550 ℃; (D) 600 ℃ biochar; (E) biochar at 650 ℃; (F) biochar at 700 ℃;
FIG. 2 is FTIR spectrum analysis of potato straw biochar;
FIG. 3 shows the effect of potato straw biochar on methane production: (A) methane solar gas production; (B) accumulating methane production;
FIG. 4 is a graph of the effect of potato straw biochar on methane content;
FIG. 5 is the effect of potato straw biochar on pH in a fermentation system;
in the figure, control: a control group; PSB: potato straw biochar group.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The potato straws used by the invention are from a Yidianhong potato variety in farms in Tianshui city, and the solid content (TS) of the straws is 95.63 +/-0.01%; volatile Solids (VS) was 69.91. + -. 0.01%. The cow dung is from a dairy farm around Lanzhou city, the solid content is 29.23 +/-0.03 percent, and the Volatile Solid (VS) is 16.51 +/-0.02 percent.
Preparation process of potato straw
(1) Firstly, cutting potato straws into small sections with the length of 2.5-3.5cm by using scissors, washing the small sections with water for several times, and washing off dust, impurities and the like on the surfaces of the straws;
(2) Placing the mixture in an outdoor drying and ventilating place for natural air drying, and then placing the mixture in an oven for drying 8 h at 60 ℃;
(3) Putting the dried potato straws into a grinder for grinding, wherein the adding amount of the straws is half of the capacity of the grinder, so as to prevent incomplete grinding, overheating of the machine and the like, and grinding the potato straws into particles with the particle size of 0.4-0.5mm;
(4) The crushed potato straws are put into a crucible, which accounts for about 1/2 of the volume of the crucible, and 4 groups are made, wherein the mass of the straws weighed in each group is shown in table 1.
TABLE 1 weighing of potato straw in crucibles
2. Baking step of potato straw biochar
(1) Weighing the mass of an empty crucible, putting the crushed straws (4 groups of weighing amounts in table 1) in a 100mL porcelain crucible, weighing the crucible mass again after compacting, and then putting the crucible in a muffle furnace for anoxic carbonization;
(2) Setting a temperature rising program and a temperature lowering program: the heating and cooling rate is 10 ℃/min, and the heating and cooling process comprises the following steps: 250. 5min at the temperature; 300. 10 min at the temperature; 400. 15 min at the temperature; 550. 5min at the temperature; 600. 2h deg.C; 550. 25min at the temperature; 480. 25min at the temperature; 380. 30min at the temperature; 280. 30min at the temperature; and finally, cooling to room temperature, taking out, and sealing for storage.
Characteristics of biochar
3.1 Basic physicochemical properties of biochar
The characteristic data of the biochar prepared by the above method are shown in the following table 2.
TABLE 2 characteristic parameters of biochar
The data in table 2 show that the potato biochar prepared by the method of the invention has larger specific surface area and higher cation exchange capacity, and is beneficial to the transfer of electrons in an anaerobic digestion system. In addition, the pH value is higher, so that acidification in the fermentation process is relieved, the pH balance in a fermentation system is maintained, and the characteristics are favorable for increasing the yield of anaerobic fermentation biogas.
3.2 Scanning electron microscope for observing surface of biochar
After pyrolysis, the substance components of the potato straws are damaged, and the structure is burnt into a more compact pore structure. The biochar prepared at the maximum temperature of 600 ℃ has the largest specific surface area, high content of micropores of the biochar and rich functional groups, and can better help microorganisms to attach so as to stabilize the anaerobic fermentation of a system. The surface morphology of the prepared biochar is shown in figure 1.
The surface structure of each biochar is observed by a scanning electron microscope in fig. 1, and the biochar pyrolyzed at different temperatures is irregular in shape. The biochar is obtained by burning under the anaerobic condition, the temperature is lower at 450-500 ℃, the cracking degree of potato straws is not enough, the straws start to be carbonized and cracked at 550 ℃, but the cracking degree is not lower than 600 ℃, the biochar pyrolyzed at 600 ℃ has more and dense surface pores, a fiber tubular structure is relatively complete, the surface damage and collapse degree is relatively lower, and the biochar is beneficial to the growth and the propagation of microorganisms to stabilize an anaerobic fermentation system, namely to increase the yield of methane. At 650 ℃, the surface of the straw biochar begins to be damaged and collapsed due to overhigh temperature, and under the pyrolysis condition of 700 ℃, the fiber tubular structure of the biomass is seriously damaged, large-area damage, collapse and other phenomena are formed, and the internal structure can be observed.
3.3 Functional group analysis of biochar
FTIR analysis of functional groups of potato straw biochar prepared by the present invention is shown in FIG. 2. As can be seen from the figure, the potato straw biochar is rich in aromatic groups and hydroxyl groups (3727.96-3415.56 cm) −1 ）、C-O、-CH、CH 2 、-CH 3 And aliphatic CH n （2945–2916 cm −1 ). The abundant functional groups are beneficial to electron transfer, enhance the electron transfer between acetogenic bacteria and methanogenic bacteria, and promote the degradation of organic matters and the generation of methane in anaerobic fermentation; on the other hand, the biochar contains a large number of amino groups, and the introduction of the N-containing functional groups can enhance the CO-pair effect of the biochar accelerator for a fermentation system added with the biochar accelerator 2 To accelerate CO in the CO-fermentation system 2 To promote CO consumption 2 To CH 4 The transformation of (3).
Application of potato straw biochar in anaerobic fermentation
4.1 Fermentation system filler
Putting potato straw biochar, cow dung and tap water into a fermentation tank for fermentation (the total solid weight of the cow dung accounts for 6.2% of the total fermentation system, the tap water accounts for 95% of the total volume of the whole fermentation system, the addition amount of the potato straw biochar relative to the whole fermentation system is 10 g/L), the total solid weight in the fermentation system is 8%, the fermentation temperature is 38 ℃, the ratio of the hollow gas volume to the effective fermentation volume of the fermentation tank is 1. The blank control group was not biochar, and the other conditions were as above. And strictly sealing after the filling is finished, and measuring the gas production and the methane content every day.
4.2 influence of biochar on daily and cumulative gas production
The daily and cumulative methane production for the placebo and charcoal groups is shown in figure 3. The daily biogas yield of the blank control group is lower than that of the experimental group and the biogas production performance is unstable, but harmful substances (acid, ammonia, nitrogen and the like) generated in the anaerobic fermentation process are accumulated to cause instability of microorganisms in the system, namely the biogas production amount is relatively small, and the daily biogas yield tends to increase firstly and then decrease and then tends to be gentle. The accumulated methane yield of the biochar group is higher than that of a control group, the daily methane yield of the biochar is relatively stable in the early stage of fermentation (14 days ago), the yield is high, and the maximum daily methane yield is 52.87 mL/g VS (6 days). The average daily gas production of the biochar group was higher than that of the control group. As can be seen from fig. 3A, in the blank control group anaerobic fermentation system, the methane yield reaches a peak value at day 5, and in the biochar group anaerobic fermentation system, the methane yield reaches a peak value at day 6, because biochar provides a survival support for microorganisms, methanogens can continuously and stably produce methane under anaerobic conditions, and then the methane yield in the anaerobic fermentation system gradually decreases after metabolic wastes of the fermentation system increase.
The accumulated methane yield of the control group is 269.86 mL/g VS, the accumulated methane yield of the biochar group is 479.93 mL/g VS, the methane yield is increased by 1.78 times, and the methane production efficiency is obviously improved.
4.3 Effect of biochar on methane content
The methane content in the biogas was determined by gas chromatography, and the results are shown in fig. 4. The average methane content of the control group is 59.0%, and the average methane content of the biochar group is 67.9%, so that the potato straw biochar serving as an additive can obviously improve the yield and the content of methane, promote biomass to be converted into clean energy and have potential application value in an anaerobic fermentation system.
4.4 Effect of biochar on pH in fermentation systems
The change of pH value in the fermentation system is shown in FIG. 5, and the pH value in the fermentation system added with charcoal is higher than that in the control group. As can be seen from the figure, the pH value rapidly decreases at the beginning of anaerobic fermentation, but the biochar group begins to rise again after day 3 and is kept at about 7.2, while the pH value of the control group slowly rises and is kept at about 6.7 after day 7, so that the rancidity phenomenon of the control group is observed at the early stage of the experiment, the control group is delayed to return to the normal level in the fermentation period, and the proper value of methane production activity can not be reached under the low-acidity environmental condition, so that the activity of methanogens is greatly inhibited, and the methane yield of the fermentation is low. Therefore, the potato straw biochar can stabilize the pH value of the fermentation system, and a self-recovery mechanism exists in the fermentation system so as to stabilize the pH value of the fermentation system, thereby increasing the yield of methane in the fermentation system.
4.5 Influence of biochar on microbial community structure in fermentation system
4.5.1 Effect of biochar on bacterial colony Structure in fermentation systems
To examine the effect of biochar on the structural composition of bacterial communities, 16S rDNA amplicon sequences were used to analyze bacterial communities in anaerobic fermentation systems. The bacterial community diversity analysis is shown in the table 3 (Con: a control group; PSB: a potato straw biochar group), and compared with the control group, the biochar group has a larger shannon index and a smaller simpson index, which indicates that the biochar group has higher biological diversity; the charo index of the biochar group is also higher, which indicates that the abundance of the community is high; therefore, the bacterial diversity and abundance of the biochar group are higher than those of the control group, which indicates that the biochar is added to be beneficial to the attachment, reproduction and growth of microorganisms.
TABLE 3 bacterial community diversity index
Bacterial colony analysis at the phylum level is shown in table 4. The most abundant phylum of bacteria in the biochar group is firmicutes, followed by bacteroidetes,CloacimonadotaAnd spirochete gate. The dominant phyla of the control group included firmicutes, bacteroidetes and actinomycetes. In the charcoal group compared with the control groupCloacimonadotaAndSpirochaetotathere was a significant difference in the relative abundance of (c). In particular, in the biochar groupCloacimonadotaThe abundance is higher than that of the control group. Firmicutes are hydrolytic bacteria that degrade some proteins and carbohydrates; it can also produce some key enzymes (e.g., proteases, celluloses, hemicelluloses, and lipases) that promote the breakdown of organic matter. This result indicates that the addition of biochar significantly alters the microbial community composition in the anaerobic fermentation system. The biochar can increase the buffer capacity, provide a microbial habitat and promote the electron transfer between methanogens and digestive bacteria, thereby improving the performance of anaerobic fermentation.
TABLE 4 bacterial community structural composition at the level of the phylum
The composition of the bacterial community at the genus level is analyzed in Table 5, and the dominant genus is shown in all samplesHydrogenisporaOf the biochar groupTuricibacterHigher than the control group, it participates in fermentation metabolism, and the product is mainly lactic acid, playing an important role in the process of producing methane.RomboutsiaAlso have the following effectsTuricibacterSimilar trend. The biochar group had the highest abundance of bacillus, which was associated with methane production, compared to the control group.CaldicoprobacterWidely exists in anaerobic fermentation systems.
TABLE 5 bacterial community structural composition at the genus level
4.5.2 Effect of biochar on archaea community structure in fermentation System
In an anaerobic fermentation system, archaea plays a very important role in the process of producing methane, in order to further understand the influence of biochar on microorganisms deeply, the diversity and the richness of archaea are researched, specific relevant indexes are shown in table 6, compared with a control group, the shannon index of a biochar group is large, the simpson index is small, and the biological diversity of the biochar group is high; the charo index of the biochar group is high, which indicates that the abundance of the community is high; therefore, the variety and the abundance of the archaea of the biochar group are higher than those of the control group, and the addition of the biochar is beneficial to the attachment, the propagation and the growth of the archaea and the promotion of the methanogenesis.
TABLE 6 archaea community diversity index
In order to further understand the changes in microorganisms, the archaea colony was investigated at the phylum level and the results are shown in Table 7. The different groups of archaea differ. In anaerobic fermentation systems, the predominant archaeomycota isHalobacterotaAndCrenarchaeota. However, of the biochar group compared to the control groupEuryauchaeotaThe abundance is high.EuryauchaeotaIncluding many methanogenic archaea, produce methane in the animal gut.
TABLE 7 archaea community structural composition at Gate level
The results of investigating the structure of archaea colonies at the genus level are shown in Table 8. In the control group, the most abundant genus was Methanosarcina, followed by c _Bathyarchaeia. Live in lifeIn the charcoal group, methanosarcina andMethanocorpusculumthe bacterial strain is the dominant bacterial strain,Methanocorpusculumin connection with the addition of biochar and methanogenesis. Methane microspheres of biochar group (Methanosphaera) The abundance was higher than that of the control group, and this trend was similar to the total methane production. Therefore, the methane microspheres are related to the methane production.
TABLE 8 bacterial community structural composition at the genus level
In conclusion, the potato straw biochar prepared by the method can remarkably promote the yield and the output of methane, improve the utilization efficiency of biomass energy and has potential application value.
Claims (5)
1. A preparation method of potato straw biochar is characterized in that potato straws are cleaned, dried and crushed to be 0.4-0.5mm in particle size, and are placed in a muffle furnace for anoxic carbonization; the carbonization temperature rise and temperature drop process is 250 ℃ for 5min; 300. 10 min at the temperature; 400. 15 min at the temperature of; 550. 5min at the temperature; 600. 2h deg.C; 550. 25min at the temperature; 480. 25min at the temperature; 380. 30min at the temperature; 280. 30min at the temperature; the heating and cooling rates are both 10 ℃/min; and finally, cooling to room temperature, taking out, and sealing for storage.
2. The method for preparing potato straw biochar as claimed in claim 1, wherein the cleaning process comprises cutting potato straws into small segments of 2.5-3.5cm in length and washing with water.
3. The method for preparing potato straw biochar as claimed in claim 1, wherein the drying process is that the potato straw cut into small sections is naturally dried in an outdoor drying and ventilating place and then is placed into an oven to be dried.
4. The application of the potato straw biochar in an anaerobic fermentation system is characterized in that the potato straw biochar is prepared by the method in claim 1; the application method comprises the following steps: putting the potato straw biochar, the cow dung and the tap water into a fermentation tank for fermentation, wherein in a fermentation system, the adding amount of the potato straw biochar is 6-12 g/L, the weight of the cow dung solid accounts for 6-8% of the total fermentation system, and the tap water accounts for 90-95% of the total volume of the whole fermentation system; the total solid weight of the fermentation system is 8-10%, the fermentation temperature is 35-38 ℃, the ratio of the air volume of the fermentation tank to the effective fermentation volume is 1.
5. The use of potato straw biochar in an anaerobic fermentation system as claimed in claim 4, wherein the potato straw biochar is added in an amount of 10 g/L, the weight of the cow dung solid accounts for 6.2% of the total fermentation system, and the tap water accounts for 95% of the total volume of the whole fermentation system; the total solid weight of the fermentation system is 8 percent, and the fermentation temperature is 38 ℃.
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