Multi-component co-pyrolysis biochar material taking mushroom dregs as main material and preparation method of multi-component co-pyrolysis biochar material

Abstract

The invention discloses a multi-component co-pyrolysis biochar material taking mushroom dregs as a main component and a preparation method thereof, and the preparation method comprises the following steps: step 1, selecting gentamicin mushroom dregs as a main component, and wheat straw and kitchen waste as additives as substrates for preparing multi-component co-pyrolysis biochar; 2, optimizing the proportion of the three raw materials by using a mixed material design and a response surface model; step 3, performing pyrolysis at 550 DEG C, and performing oxygen-limited pyrolysis in a muffle furnace for 1 hour; 4, the yield and the specific surface area of the biochar serve as response indexes, and finally the optimal proportion of the three raw materials is obtained through model optimization. According to the prepared biochar material, the specific surface area and the pore structure of the biochar are remarkably improved, and the biochar material shows better application prospects in the fields of pollutant adsorption, soil improvement, environmental remediation and the like; through innovative raw material combination and process route, various key properties of the biochar are remarkably improved, and the biochar has wide market application value and scientific research significance.

Description

Technical Field

[0001] The invention relates to a co-pyrolysis biochar material, and in particular to a multi-component co-pyrolysis biochar material mainly composed of fungus residue and a preparation method thereof. Background Art

[0002] Gentamicin Mycelial Residue (GMR) is a by-product produced during the production of antibiotics. It contains a large amount of organic substances such as proteins, polysaccharides, and nucleic acids, and has a high potential for resource utilization. In the treatment of antibiotic industrial waste, traditional treatment methods, such as landfill and incineration, not only cause secondary pollution to the environment, but also waste the resources contained in these organic substances. In recent years, with the increasingly serious problem of solid waste management around the world, the resource utilization of GMR has gradually attracted attention, among which pyrolysis technology has become an effective resource utilization path, especially in the field of biochar preparation.

[0003] GMR is rich in organic matter, and its high nitrogen content makes the biochar generated during the pyrolysis process have a unique chemical composition. Unlike traditional lignocellulosic biomass (such as wood and straw), GMR can generate a large number of nitrogen-containing functional groups (such as carboxyl, amino and hydroxyl) during the pyrolysis process. These functional groups give biochar stronger adsorption capacity and chemical reactivity. Specifically, these nitrogen-containing functional groups can produce strong adsorption reactions with heavy metal ions, pollutant molecules, etc., making GMR biochar have broad application potential in water treatment, soil remediation and other fields. In addition, the pyrolysis temperature of GMR is relatively low, and the decomposition and conversion of organic matter can be completed under milder conditions, which not only improves energy utilization efficiency, but also reduces the cost of pyrolysis equipment.

[0004] Although GMR has the above advantages in preparing biochar, there are still some problems and shortcomings in its pyrolysis process. First, due to the low content of volatiles in GMR, less gas and volatile products are released during the pyrolysis process, resulting in poor pore structure and specific surface area of ​​the final biochar. This defect in pore structure will affect the adsorption capacity of biochar, making it less than ideal in treating pollutants. Secondly, GMR biochar has weak mechanical strength and poor structural stability, which limits its use in certain application scenarios with higher requirements, such as long-term environmental remediation and soil improvement. In addition, the carbon content generated during the pyrolysis of GMR is low, which makes the carbon retention efficiency of biochar lower than that of other biomass raw materials, which also limits its application value as a carbon sink material.

[0005] Therefore, although GMR biochar has unique advantages in some aspects, current research shows that the performance of biochar prepared using GMR alone is still insufficient, and it is urgent to further explore how to improve its performance by co-pyrolysis with other materials and optimizing the ratio of different raw materials. Summary of the invention

[0006] In view of this, the present invention provides a multi-component co-pyrolysis biochar material mainly composed of fungus residue and a preparation method thereof.

[0007] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0008] A multi-component co-pyrolysis biochar material mainly based on fungus residue and a preparation method thereof, comprising the following steps:

[0009] Step 1: Select gentamicin residue as the main component, wheat straw and kitchen waste as additives, and use them as substrates for preparing multi-component co-pyrolysis biochar;

[0010] Step 2: Optimize the ratio of the three raw materials using mixture design and response surface model;

[0011] Step 3: Pyrolysis at 550 °C in a muffle furnace with oxygen-limited pyrolysis for 1 h;

[0012] Step 4: Use the “yield” and “specific surface area” of biochar as response indicators, and finally obtain the optimal ratio of the three raw materials through model optimization.

[0013] Preferably, in step 2, there are 10 kinds of raw materials in different ratios.

[0014] Preferably, in step 2, the 10 different proportions are: gentamicin residue 0%, wheat straw 100%, and restaurant waste 0%; gentamicin residue 100%, wheat straw 0%, and restaurant waste 0%; gentamicin residue 0%, wheat straw 0%, and restaurant waste 100%; gentamicin residue 50%, wheat straw 50%, and restaurant waste 0%; gentamicin residue 0%, wheat straw 50%, and restaurant waste 50%; gentamicin residue Gentamicin residue 50%, wheat straw 0%, kitchen waste 50%; gentamicin residue 66.7%, wheat straw 16.7%, kitchen waste 16.6%; gentamicin residue 16.7%, wheat straw 16.6%, kitchen waste 66.7%; gentamicin residue 16.6%, wheat straw 16.7%, kitchen waste 66.7%; gentamicin residue 33.4%, wheat straw 33.3%, kitchen waste 33.3%.

[0015] Preferably, the fitting equations for the yield of biochar and the ratio of specific surface area to raw material finally obtained in step (4) are as shown in Formula 3-1 and Formula 3-1;

[0016] Yield = 28.37x1 + 58.55x2 + 24.83x3 - 7.28x1x2 - 3.52x1x3 + 9.95x2x3 (3-1)

[0017] Specific surface area = 109.65x1 + 121.46x2 + 0.56x3 + 201.33x1x2 - 60.48x1x3 + 379.15x2x3 (3-2).

[0018] Preferably, the optimal addition ratio of the three raw materials finally obtained after model optimization is 66.7% of gentamicin residue, 16.7% of wheat straw, and 16.6% of restaurant kitchen waste.

[0019] Preferably, under this addition ratio, the yield of the obtained biochar is 45.9% and the specific surface area is 165.86 m2 / g.

[0020] A multi-component co-pyrolysis biochar material mainly composed of fungus residue and a preparation method thereof to obtain co-pyrolysis multi-component biochar.

[0021] Compared with the prior art, the present invention has achieved the following technical effects:

[0022] (1) The biochar material prepared by the present invention significantly improves the specific surface area and pore structure of the biochar through the synergistic pyrolysis of multi-component raw materials. Compared with the biochar prepared from traditional single biomass, it exhibits superior performance in terms of adsorption performance, carbon retention capacity and microbial regulation.

[0023] (2) The present invention further verifies the pore size distribution optimization effect of the biochar of the present invention through nitrogen adsorption / desorption experiments. The pore structure of the biochar is more developed, with a more complex pore structure or higher pore connectivity. The adsorption capacity is significantly enhanced;

[0024] (3) The biochar obtained by co-pyrolysis of gentamicin residue is rich in nitrogen-based functional groups, and its porosity and surface activity are significantly improved, thus showing better application prospects in the fields of pollutant adsorption, soil improvement and environmental remediation;

[0025] (4) The present invention significantly improves the key properties of biochar through innovative raw material combination and process route, and has broad market application value and scientific research significance. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The response surface of the biochar yield under different raw material ratio conditions of a multi-component co-pyrolysis biochar material mainly based on fungus residue and a preparation method of the present invention;

[0027] Figure 2The response surface of the specific surface area of ​​biochar under different raw material ratios of a multi-component co-pyrolysis biochar material mainly based on fungus residue and a preparation method of the present invention;

[0028] Figure 3 The thermogravimetric curves of the single and co-pyrolysis processes of gentamicin residue-wheat straw-kitchen waste in the multi-component co-pyrolysis biochar material mainly based on residue and the preparation method of the present invention;

[0029] (a)TG; (b)DTG;

[0030] Figure 4 This is a scanning electron microscope photo of gentamicin residue and biochar of a multi-component co-pyrolysis biochar material mainly based on the residue and a preparation method of the present invention;

[0031] (a) Gentomycin residue; (b) Biochar from pyrolysis of the residue alone - QBC; (c) Biochar from co-pyrolysis under the optimal ratio - GBC;

[0032] Figure 5 A schematic diagram of N2 adsorption-desorption and pore size of different biochars in a multi-component co-pyrolysis biochar material mainly based on fungus residue and a preparation method of the present invention;

[0033] (a) Gentomyicin residue-based biochar - QBC; (b) co-pyrolysis biochar - GBC. DETAILED DESCRIPTION

[0034] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] The present invention discloses a multi-component co-pyrolysis biochar material mainly based on fungus residue and a preparation method thereof, comprising the following steps:

[0036] Step 1: Select gentamicin residue as the main component, wheat straw and kitchen waste as additives, and use them as substrates for preparing multi-component co-pyrolysis biochar;

[0037] Step 2: Use mixture design and response surface model to optimize 10 different ratios of the three raw materials; they are: gentamicin residue 0%, wheat straw 100%, restaurant waste 0%; gentamicin residue 100%, wheat straw 0%, restaurant waste 0%; gentamicin residue 0%, wheat straw 0%, restaurant waste 100%; gentamicin residue 50%, wheat straw 50%, restaurant waste 0%; gentamicin residue 0%, wheat straw 50%, restaurant waste 50% of gentamicin residue, 0% of wheat straw, 50% of restaurant waste; 66.7% of gentamicin residue, 16.7% of wheat straw, 16.6% of restaurant waste; 16.7% of gentamicin residue, 16.6% of wheat straw, 66.7% of restaurant waste; 16.6% of gentamicin residue, 16.7% of wheat straw, 66.7% of restaurant waste; 33.4% of gentamicin residue, 33.3% of wheat straw, 33.3% of restaurant waste;

[0038] Under this addition ratio, the yield of the obtained biochar was 45.9% and the specific surface area was 165.86 m2 / g.

[0039] Step 3: Pyrolysis at 550 °C in a muffle furnace with oxygen-limited pyrolysis for 1 h;

[0040] Step 4: The “yield” and “specific surface area” of biochar are used as response indicators, and the optimal ratio of the three raw materials is finally obtained through model optimization;

[0041] Finally, the fitting equations of biochar yield and specific surface area to raw material ratio are shown in Formula 3-1 and Formula 3-1;

[0042] Yield = 28.37x1 + 58.55x2 + 24.83x3 - 7.28x1x2 - 3.52x1x3 + 9.95x2x3 (3-1)

[0043] Specific surface area = 109.65x1 + 121.46x2 + 0.56x3 + 201.33x1x2 - 60.48x1x3 + 379.15x2x3 (3-2);

[0044] After model optimization, the optimal addition ratio of the three raw materials was 66.7% of gentamicin residue, 16.7% of wheat straw, and 16.6% of restaurant kitchen waste. Figure 1 and Figure 2 shown.

[0045] Embodiment 1:

[0046] Gentamicin residue, wheat straw and restaurant kitchen waste were mixed in proportions of 66.7%, 16.7% and 16.6% to obtain mixed raw material 1; then the addition ratio of gentamicin residue was adjusted to 100%, named 2; the addition ratio of wheat straw was adjusted to 100%, named 3; the addition ratio of restaurant kitchen waste was adjusted to 100%, named 4. The four raw materials with different proportions were used for thermogravimetric analysis.

[0047] Under nitrogen protection, the above raw materials 1, 2, 3, and 4 were placed in a thermogravimetric analyzer respectively, with a heating rate of 10°C / min and a temperature range of 30°C to 900°C. The weight loss of each sample at different temperatures was recorded, and its pyrolysis characteristic parameters were analyzed, including the initial pyrolysis temperature, the maximum pyrolysis rate temperature, the residual carbon rate, etc. The experimental results show that there are significant differences in the pyrolysis behavior of raw materials with different ratios. Under co-pyrolysis conditions, the initial pyrolysis temperature was lower than that of the pyrolysis of single-component fungus residue. The temperature of the maximum weight loss rate peak shifted to the left, and the corresponding temperature was 19.59°C lower than that of the pyrolysis of the fungus residue alone. The above analysis shows that the addition of wheat straw and kitchen waste can promote the pyrolysis process of gentamicin fungus residue, and there is a certain positive synergistic effect between the substances; such as Figure 3 (a), (b) and Table 1.

[0048] Table 1: Thermal decomposition parameters of raw materials with different ratios

[0049]

[0050] Embodiment 2:

[0051] Gentamicin residue, wheat straw and food waste were mixed evenly in the proportion of 66.7%, 16.7% and 16.6% to obtain a co-pyrolysis raw material mixture; then the mixture was placed in a muffle furnace and pyrolyzed at 550°C for 1h under oxygen-limited conditions. After the pyrolysis was completed, the product was rinsed with distilled water to remove impurities and then dried at 105°C to constant weight. After drying, the sample was sieved through a 60-mesh sieve, and the sieved sample was sealed in a sealed bag to obtain co-pyrolysis biochar (GBC).

[0052] The addition ratio of gentamicin residue was adjusted to 100%, and the above steps were repeated to prepare single-component gentamicin residue-based biochar (QBC).

[0053] Scanning electron microscope (SEM) analysis was performed on the above two biochars to observe the changes in their surface morphology. The experiment showed that the surface morphology of GBC and QBC showed obvious differences. The pore structure in GBC was more developed, while the surface of QBC was denser and had fewer pores. Figure 4 (a), (b), (c) and Table 2.

[0054] Table 2: Thermal decomposition parameters of raw materials with different ratios

[0055]

[0056] Embodiment 3:

[0057] Gentamicin residue, wheat straw and food waste were mixed in a ratio of 66.7%, 16.7% and 16.6% to obtain a co-pyrolysis raw material; the mixture was placed in a muffle furnace and pyrolyzed at 600°C for 1 hour under oxygen-limited conditions. After the pyrolysis was completed, the product was rinsed with distilled water to remove residual impurities on the surface, and then dried at 105°C to constant weight. After drying, the sample was sieved through a 60-mesh sieve, and the co-pyrolysis biochar (GBC) obtained was sealed in a sealed bag for later use.

[0058] The addition ratio of gentamicin residue was adjusted to 100%, and the same steps were repeated to prepare single-component gentamicin residue-based biochar (QBC).

[0059] The specific surface area and pore size distribution of GBC and QBC prepared as above were analyzed. The pore structure of biochar was characterized by nitrogen adsorption / desorption experiment (N2 desorption method), and the specific surface area was calculated by BET (Brunauer-Emmett-Teller) method, and the distribution and change of biochar pore size were analyzed. The experimental results show that there are significant differences in the pore structure of biochars with different ratios. The pore structure of GBC is more developed, while the pore size of QBC is relatively small and the distribution is more concentrated; Figure 5 As shown in (a) and (b).

[0060] The above description is only a preferred embodiment of the present invention and does not limit the technical scope of the present invention. Therefore, any slight modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A multi-component co-pyrolysis biochar material mainly based on fungus residue and a preparation method thereof, characterized in that: The following steps are involved: Step 1: Select gentamicin residue as the main component, wheat straw and kitchen waste as additives, and use them as substrates for preparing multi-component co-pyrolysis biochar; Step 2: Optimize the ratio of the three raw materials using mixture design and response surface model; Step 3: Pyrolysis at 550 °C in a muffle furnace with oxygen-limited pyrolysis for 1 h; Step 4: The "yield" and "specific surface area" of biochar are used as response indicators, and finally the optimal ratio of the three raw materials is obtained through model optimization.

2. The multi-component co-pyrolysis biochar material mainly based on fungus residue and the preparation method according to claim 1, characterized in that: In step 2, there are 10 kinds of raw materials with different ratios.

3. The multi-component co-pyrolysis biochar material mainly based on fungus residue and the preparation method according to claim 2, characterized in that: In step 2, the 10 different proportions are: gentamicin residue 0%, wheat straw 100%, and restaurant waste 0%; gentamicin residue 100%, wheat straw 0%, and restaurant waste 0%; gentamicin residue 0%, wheat straw 0%, and restaurant waste 100%; gentamicin residue 50%, wheat straw 50%, and restaurant waste 0%; gentamicin residue 0%, wheat straw 50%, and restaurant waste 50%; gentamicin residue Fungus residue 50%, wheat straw 0%, kitchen waste 50%; gentamicin fungus residue 66.7%, wheat straw 16.7%, kitchen waste 16.6%; gentamicin fungus residue 16.7%, wheat straw 16.6%, kitchen waste 66.7%; gentamicin fungus residue 16.6%, wheat straw 16.7%, kitchen waste 66.7%; gentamicin fungus residue 33.4%, wheat straw 33.3%, kitchen waste 33.3%.

4. The multi-component co-pyrolysis biochar material mainly based on fungus residue and the preparation method according to claim 1, characterized in that: The fitting equations for the yield of biochar and the ratio of specific surface area to raw material finally obtained in step (4) are shown in Formula 3-1 and Formula 3-1; Yield = 28.37x1 + 58.55x2 + 24.83x3 - 7.28x1x2 - 3.52x1x3 + 9.95x2x3 (3-1) Specific surface area = 109.65x1 + 121.46x2 + 0.56x3 + 201.33x1x2 - 60.48x1x3 + 379.15x2x3 (3-2).

5. The multi-component co-pyrolysis biochar material mainly based on fungus residue and the preparation method according to claim 1, characterized in that: After model optimization, the optimal addition ratio of the three raw materials was 66.7% of gentamicin residue, 16.7% of wheat straw, and 16.6% of restaurant waste.

6. The multi-component co-pyrolysis biochar material mainly based on fungus residue and the preparation method according to claim 5, characterized in that: Under this addition ratio, the yield of the obtained biochar was 45.9% and the specific surface area was 165.86 m2 / g.

7. Co-pyrolysis multi-component biochar obtained according to the method according to any one of claims 1 to 6.

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