Biomass oil sludge pyrolysis residue rich in enzyme as well as preparation method and application of biomass oil sludge pyrolysis residue

Abstract

The invention relates to the technical field of oil sludge pyrolysis residue recycling, in particular to enzyme-rich biomass oil sludge pyrolysis residues as well as a preparation method and application thereof. According to the method, the oil sludge pyrolysis residues are improved in a biomass mode, specifically, the ratio of the oil sludge pyrolysis residues to the biomass to the livestock and poultry manure is regulated and controlled, so that a composting system reaches a proper C / N ratio, biomass of the oil sludge pyrolysis residues is achieved, and a residue product rich in enzyme is obtained. The residue has rich pore structures and organic matters, and can be used as a green organic fertilizer for soil improvement and plant cultivation.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oil sludge pyrolysis residue resource, and particularly relates to a biomass-enzymed oil sludge pyrolysis residue and a preparation method and application thereof. BACKGROUND

[0002] Oil sludge is a kind of oil-containing solid waste generated in the process of oil exploitation, transportation, refining and accidents. Due to its combustion characteristics and the presence of biological toxic substances, it is listed as a hazardous solid waste in China. However, the presence of petroleum hydrocarbons endows oil sludge with resource properties. Pyrolysis technology has multiple advantages such as high efficiency, high harmlessness, and resource recovery for oil sludge treatment and disposal. According to the existing oil sludge accumulation, it is estimated that 800 million tons of pyrolysis residue will be generated through pyrolysis treatment of oil sludge, which urgently needs further treatment and application. Therefore, if a large amount of oil sludge pyrolysis residue cannot be further disposed of efficiently and safely, it will not only occupy a large amount of land resources, but also may damage the soil environment, cause plant poisoning, and even threaten environmental health.

[0003] At present, the utilization ways of oil sludge pyrolysis residue resource include building materials, construction landfill soil, landfill soil, and adsorbent with high added value. However, the use of building materials and adsorbents has the disadvantages of low energy efficiency and poor acceptance. Oil sludge pyrolysis residue contains part of inorganic components similar to soil, so entering the soil is a potential disposal way. However, due to poor physicochemical properties and low nutrient content, it is difficult to achieve the improvement effect of soil positive effect and "soil treatment with soil".

[0004] Using oil sludge pyrolysis residue as green organic fertilizer not only solves the problem of harmful storage of oil sludge pyrolysis residue, but also realizes the reuse of oil sludge pyrolysis residue. However, the physicochemical properties of oil sludge pyrolysis residue itself are not suitable for use as plant growth soil, which not only cannot provide nutrients for plants, but also causes plants to accumulate heavy metals. Therefore, how to utilize oil sludge pyrolysis residue so that it can be used as green organic fertilizer is a difficult problem. SUMMARY

[0005] The present application provides a biomass-enzymed oil sludge pyrolysis residue and a preparation method and application thereof. The present application uses biomass to improve oil sludge pyrolysis residue. The biomass-enzymed oil sludge pyrolysis residue is rich in enzymes, has rich pore structure and a large amount of organic matter, and can be used as green organic fertilizer.

[0006] In order to achieve the above purpose, the present application provides the following technical scheme: The application provides a method for preparing enzyme-rich biomassized oil sludge pyrolysis residue, which comprises the following steps: adding biomass and livestock and poultry manure into oil sludge pyrolysis residue to obtain compost raw materials, and then performing composting treatment to obtain enzyme-rich biomassized oil sludge pyrolysis residue; the initial carbon-nitrogen ratio of the compost raw materials is (24-26):1.

[0007] The oil sludge pyrolysis residue is the best treatment method for entering the soil, but the physical and chemical properties are poor and the organic matter content is low, so it is difficult to realize the positive effect of soil improvement and the improvement effect of "soil treating soil". Moreover, the oil sludge pyrolysis residue has the characteristics of low carbon-nitrogen ratio, so by introducing biomass and livestock and poultry manure with high carbon and low nitrogen to adjust the carbon-nitrogen ratio, the feasibility of the compost biomassized oil sludge pyrolysis residue can be significantly improved.

[0008] However, in the experimental process of the present application, it is found that under a specific carbon-nitrogen ratio, the oil sludge pyrolysis residue, biomass and livestock and poultry manure compost fermentation can complete the complete biomassization of the oil sludge pyrolysis residue. In addition, when the carbon-nitrogen ratio is controlled to be 24-26, the obtained biomassized oil sludge pyrolysis residue is rich in urease and invertase. Urease catalyzes the hydrolysis of urea into ammonia (NH3) and carbon dioxide, which is the core enzyme of soil nitrogen cycle. Invertase can catalyze the hydrolysis of sucrose into glucose and fructose, which drives the soil carbon cycle. The enzyme content and enzyme activity are greatly improved, which can help to increase the microbial community abundance and provide more microbial activity for plant growth.

[0009] At the same time, after the biomassization of the oil sludge pyrolysis residue, the organic matter is improved, and the organic matter content is higher than that of general biomass organic fertilizer. This shows that the method provided by the present application can not only realize the real biomassization of the oil sludge pyrolysis residue, but also can replace the general biomass organic fertilizer.

[0010] Preferably, the initial carbon-nitrogen ratio of the compost raw materials is 25:1.

[0011] Preferably, the biomass is at least one of corn stalks, fallen leaves, rice husks and peanut shells.

[0012] Preferably, the particle size of the biomass is 20-40 mesh.

[0013] Preferably, the livestock and poultry manure is at least one of pig manure, sheep manure, chicken manure, duck manure and cow manure.

[0014] Preferably, the mass ratio of the oil sludge pyrolysis residue, biomass and livestock and poultry manure is (10-14):1:3.

[0015] More preferably, the mass ratio of the oil sludge pyrolysis residue, corn stalks and pig manure is (10-14):1:3.

[0016] Preferably, the composting treatment time is 4-5 weeks.

[0017] The present application provides an enzyme-rich biomass-oil sludge pyrolysis residue, which has a pore structure.

[0018] Preferably, in the enzyme-rich biomass-oil sludge pyrolysis residue, the urease content is 9000-10000 μg / d / g, and the invertase content is 135-145 mmol / d / g.

[0019] The present application provides a soil greening substrate, which comprises an enzyme-rich biomass-oil sludge pyrolysis residue and a soil substrate; the addition ratio of the enzyme-rich biomass-oil sludge pyrolysis residue is 2-5 wt% based on the weight of the soil substrate.

[0020] The present application provides an application of the soil greening substrate in cultivating energy plants, and the energy plants are Arundo donax, alfalfa or tall fescue.

[0021] Therefore, the present application has the following beneficial effects: (1) The present application uses high-carbon and low-nitrogen biomass, livestock and poultry manure, and low-carbon and nitrogen ratio oil sludge pyrolysis residue for compounding, and uses the biomass, livestock and poultry manure auxiliary composting technology to biomass the oil sludge pyrolysis residue.

[0022] (2) The present application regulates the ratio between the oil sludge pyrolysis residue and the pig manure and the corn straw, so that the C / N ratio is appropriate, so as to realize the complete biomass of the oil sludge pyrolysis residue, and finally obtain the enzyme-rich biomass-oil sludge pyrolysis residue with excellent performance.

[0023] (3) The enzyme-rich biomass-oil sludge pyrolysis residue obtained by the present application contains a large amount of urease and invertase, and retains a multi-level pore structure by means of the loose and porous oil sludge pyrolysis residue and corn straw, and contains a large amount of organic matter, which can replace general organic fertilizer for use. The rich pore structure facilitates the exchange of microorganisms, so that the application effect of the organic fertilizer is better.

[0024] (4) The present application realizes the biomass of the oil sludge pyrolysis residue, not only solves the problem of harmful storage of the oil sludge pyrolysis residue, but also realizes the resource reutilization to convert the oil sludge pyrolysis residue into green organic fertilizer. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The urease content in different composts.

[0026] Figure 2 The acid phosphatase, catalase and invertase contents in different composts.

[0027] Figure 3 The total organic matter content in different composts.

[0028] Figure 4 Figure 6 is a Raman spectrum analysis result chart.

[0029] Figure 5 Figure 7 is a SEM and fluorescence microscope result chart, (h-1), (h-2) correspond to E after composting, (i-1), (i-2) correspond to B after composting, (j-1), (j-2) correspond to B before composting.

[0030] Figure 6 Figure 8 is a carbon-nitrogen ratio change result chart at different periods.

[0031] Figure 7 Figure 9 is a pH value change result chart at different periods.

[0032] Figure 8 Figure 10 is a cation exchange capacity change result chart at different periods.

[0033] Figure 9 Figure 11 is a three-dimensional fluorescence spectrum comparison of composting, (a) control group-water sample, (b) composting B.

[0034] Figure 10 Figure 12 is a growth index of reed, alfalfa and tall fescue in different soils, (a) is the statistical data of reed, (b) is the statistical data of alfalfa, (c) is the statistical data of tall fescue, (d) is the statistical data of reed.

[0035] Figure 11 Figure 13 is a growth index of reed, alfalfa and tall fescue in different soils, (e) is the statistical data of alfalfa, (f) is the statistical data of tall fescue, (g) is the crude fat of reed in different soils, (h) is the content of chlorophyll a and b in reed, (i) is the content of cellulose, hemicellulose and lignin in reed.

[0036] Figure 12 Figure 14 is a plant growth index change trend chart, (a) is a comparison chart of composting performance and plant growth trend under different mixing ratios, (b) is bulk density, (c) is water holding capacity, (d) is cation exchange capacity, (e) is N / P / K content, (f) is soil organic matter.

[0037] Figure 13 Figure 15 is a plant growth index change trend chart, (g)-(h) are soil enzyme activity and content.

[0038] Figure 14 Figure 16 is a bacterial community distribution chart of DS-1 and DS-2.

[0039] Figure 15 Figure 17 is a fungal community distribution chart of DS-1 and DS-2.

[0040] Figure 16 Figure 18 is a comparison of different protein metabolism pathways.

[0041] Figure 17 Bar chart for EggNOG functional group annotation results.

[0042] Figure 18 Venn diagram for species.

[0043] Figure 19 Abundance level curve for different levels. DETAILED DESCRIPTION

[0044] The application will be further described below with reference to the specific examples. Those skilled in the art can implement the application based on the description. In addition, the examples of the application involved in the following description are generally only examples of a part of the application, not all examples. Therefore, based on the examples in the application, all other examples obtained by those skilled in the art without creative labor shall fall within the scope of protection of the application.

[0045]

EXAMPLE

[0046] (2) According to the C and N contents in the corn straw, pig manure and oil sludge pyrolysis residues, 1.5 kg of corn straw, 0.5 kg of pig manure and 6 kg of oil sludge pyrolysis residues were weighed to obtain the compost raw material, and the initial C / N ratio of the oil sludge pyrolysis residues was adjusted to 25.

[0047] (3) 1000 mL of water was added to the compost raw material, which was exposed to air for aerobic composting fermentation for 28 days to prepare the biomass oil sludge pyrolysis residue rich in enzymes, which was recorded as compost group B.

[0048] Table 1 Composition analysis of compost raw material

[0049] Comparative Example 1 (1) The corn straw and pig manure shown in Table 1 were placed in a blast drying oven, kept at 105°C for 24 h, crushed by a crusher and then sieved through a 20-mesh sieve for use.

[0050] (2) According to the C and N contents in the corn straw and pig manure, 1.5 kg of corn straw and 0.5 kg of pig manure were weighed to obtain the compost raw material, and the initial C / N ratio of the compost raw material was adjusted to 40.

[0051] (3) 1000 mL of water was added to the compost raw material, which was exposed to air for aerobic composting fermentation for 28 days to prepare the biomass oil sludge pyrolysis residue rich in enzymes, which was recorded as compost group B.

[0052] Comparative Example 2 (1) The corn stalks, pig manure, and oil sludge pyrolysis residues shown in Table 1 were placed in a blast drying oven, kept at 105°C for 24 h, crushed by a pulverizer, and sieved through a 20-mesh sieve for use.

[0053] (2) Based on the C and N contents in the corn stalks, pig manure, and oil sludge pyrolysis residues, 1.5 kg of corn stalks, 0.5 kg of pig manure, and 10 kg of oil sludge pyrolysis residues were mixed to obtain compost raw materials, and the initial C / N ratio of the oil sludge pyrolysis residues was adjusted to 20.

[0054] (3) 1000 mL of water was added to the compost raw materials, which were exposed to air for aerobic composting fermentation for 28 days to produce biomass-converted oil sludge pyrolysis residues, which were recorded as Compost Group A.

[0055] Comparative Example 3 (1) The corn stalks, pig manure, and oil sludge pyrolysis residues shown in Table 1 were placed in a blast drying oven, kept at 105°C for 24 h, crushed by a pulverizer, and sieved through a 20-mesh sieve for use.

[0056] (2) Based on the C and N contents in the corn stalks, pig manure, and oil sludge pyrolysis residues, 1.5 kg of corn stalks, 0.5 kg of pig manure, and 2 kg of oil sludge pyrolysis residues were mixed to obtain compost raw materials, and the initial C / N ratio of the oil sludge pyrolysis residues was adjusted to 30.

[0057] (3) 1000 mL of water was added to the compost raw materials, which were exposed to air for aerobic composting fermentation for 28 days to produce biomass-converted oil sludge pyrolysis residues, which were recorded as Compost Group C.

[0058] Comparative Example 4 (1) The corn stalks, pig manure, and oil sludge pyrolysis residues shown in Table 1 were placed in a blast drying oven, kept at 105°C for 24 h, crushed by a pulverizer, and sieved through a 20-mesh sieve for use.

[0059] (2) Based on the C and N contents in the corn stalks, pig manure, and oil sludge pyrolysis residues, 1.5 kg of corn stalks, 0.5 kg of pig manure, and 0.67 kg of oil sludge pyrolysis residues were mixed to obtain compost raw materials, and the initial C / N ratio of the oil sludge pyrolysis residues was adjusted to 35.

[0060] (3) 1000 mL of water was added to the compost raw materials, which were exposed to air for aerobic composting fermentation for 28 days to produce biomass-converted oil sludge pyrolysis residues, which were recorded as Compost Group D.

[0061]

Performance Test

[0062] Figure 1 and Figure 2 The effect of different compost ratios on enzyme content in compost, and the enzyme species and high activity in compost are mainly urease (S-UE), acid phosphatase (S-ACP), catalase (S-CAP), and sucrose (S-SC). The enzyme content in compost B group is the highest, and the contents of S-UE, S-ACP, S-CAP, and S-SC are 9310 μg / d / g, 17.9 μg / d / g, 66.5 μg / d / g, and 139.0 μg / d / g, respectively. Notably, the S-UE and S-SC in the compost B group are significantly higher than those in the compost E group (without adding oil sludge pyrolysis residue group), which indicates that the oil sludge pyrolysis residue and pig manure and corn straw have a special effect at a specific ratio, resulting in a significant increase in the content of S-UE and S-SC. S-UE can promote the generation of carbon dioxide, ammonia, and CO2 from organic matter and urea; and S-SC further converts sucrose into glucose and fructose, etc. In addition, when the ratio between oil sludge pyrolysis residue and pig manure and corn straw is not appropriate, resulting in an unsuitable C / N ratio, the addition of oil sludge pyrolysis residue significantly reduces the content of S-UE.

[0063] Figure 3 The effect of different compost ratios on the organic matter content in compost. The organic matter contents of compost A, compost B, compost C, compost D, and compost E are 327.6 g / kg, 384.3 g / kg, 351.9 g / kg, 348.2 g / kg, and 367.2 g / kg, respectively. Among them, except for the compost B group, the organic matter contents of compost A, C, and D are lower than that of the compost E group without adding oil sludge pyrolysis residue. This indicates that the physicochemical properties of oil sludge pyrolysis residue itself determine that it is not suitable for use as organic fertilizer alone, and when it is treated by biomassization with corn straw and pig manure, which are common organic fertilizer raw materials, it cannot achieve the performance equivalent to that of conventional organic fertilizer. Instead, due to the characteristics of oil sludge pyrolysis residue, the performance of the compost prepared is not as good as that obtained by direct fermentation of corn straw and pig manure. Therefore, the selection of the initial C / N ratio in the compost raw materials (i.e., the ratio between oil sludge pyrolysis residue and pig manure and corn straw) is the key to regulating and achieving complete biomassization of oil sludge pyrolysis residue.

[0064] The above conclusions all indicate that biomassization of oil sludge pyrolysis residue cannot be achieved simply by adding pig manure and corn straw, and it is necessary to regulate the ratio between oil sludge pyrolysis residue and pig manure and corn straw to make the C / N ratio appropriate, so as to achieve complete biomassization of oil sludge pyrolysis residue, and ultimately obtain biomassized oil sludge pyrolysis residue rich in enzymes with excellent performance.

[0065] Further, the morphology structure of the physical structure of the composting process was characterized before and after composting, and the results of compost B- (before composting), compost B and compost E are shown in Figure 4 and Figure 5 It can be observed that the I Figure 4 / I D / I G of the compost B-, compost B and compost E are 0.89, 0.87 and 0.90, respectively. This shows that after the biomass of the oil sludge pyrolysis residue is fermented by corn straw and pig manure composting, it still has a rich pore structure, and compared with the compost E group, the I D / I G ratio does not decrease significantly. This result shows that the addition of the oil sludge pyrolysis residue does not destroy the pore structure of the corn straw / pig manure organic fertilizer, and the loose and porous structure of the oil sludge pyrolysis residue itself can further promote the respiratory degradation of microorganisms to produce more organic matter, which can help the final compost B to have a multi-level pore structure and higher content of organic matter. Figure 5 The SEM results also verify the results in Figure 4 , and the compost B group has a more abundant pore after composting.

[0066] 2. Application potential The biomass of the oil sludge pyrolysis residue obtained by aerobic fermentation of Example 1 under different composting periods (0 weeks, 1 week, 2 weeks, 3 weeks, 4 weeks, 5 weeks) was explored. The corrosion process of the biomass of the oil sludge pyrolysis residue in the aerobic fermentation process is shown in Figures 6-8 .

[0067] As shown in Figure 6 , the C / N ratio at different composting periods was calculated according to the elemental analysis results to reflect the corrosion process of the organic fertilizer. Overall, with the deepening of the composting process, the C / N ratio in the composting gradually decreased, and the C / N ratio in the early composting stage (the first week) and the maturation stage (the third week) basically slowed down and tended to be stable. The main factors affecting the C / N ratio are the changes in total organic carbon (TOC) and total nitrogen (TN) content. During the entire composting process, the TOC content will decrease continuously as the microorganisms decompose organic matter, and the TN will decrease due to the emission of a large amount of NH3 in the early stage of composting. In the middle and late stages of composting, the organic matter in the composting will be rapidly degraded, and the degradation of nitrogen-containing organic matter and the reduction of the total amount of materials will further promote the accumulation of TN, which leads to a gradual decrease in the C / N ratio in the middle stage. In the later composting process (after 21 days), the internal temperature gradually decreases, the decomposition of organic materials gradually slows down, and various factors such as the intensification of nitrification and denitrification and the emission of N2O lead to a slow change and stabilization of the C / N ratio. Finally, the C / N ratio stabilizes at 16, which meets the maturation requirements of organic fertilizer.

[0068] As shown in Figure 7 , the compost pH shows a trend of first rising, then falling and then rising again, which can directly reflect the survival condition of microorganisms in the compost process. Generally, the optimal pH value for the survival, reproduction and metabolism of microorganisms is neutral and weakly alkaline. The change of pH in the compost is mainly caused by the combined action of organic acids and ammonia produced by carbon-containing organic matter and nitrogen-containing organic matter. The main reason for the rise of pH in the early stage is that the ammonification promotes the decomposition of protein to generate ammonia gas, resulting in the rise of pH, and the subsequent fall of pH indicates that the degree of acidification is deepened, which is mainly caused by the release of acidic and decarboxylation during the carbonization process, resulting in the increase of surface acidic functional groups.

[0069] Figure 8 The cation exchange capacity of compost in different periods is shown, which can reflect the nutrient capacity, inorganic salt ion buffering performance and organic matter change of the compost in real time. Compared with the initial value, the value in the compost B shows a trend of increasing to different degrees, which reversely proves the increase of stable organic matter. The increase of cation exchange capacity refers to the content and capacity of exchangeable cations, the accumulation of compounds containing negative charges (such as lignocellulose derived products or carboxyl and phenolic hydroxyl groups, etc.). The increase of cation exchange capacity proves the retention of nutrients, while avoiding leaching into groundwater.

[0070] The above results show that the method provided by the present application promotes the decomposition and transformation of organic matter to organic matter and protein in the compost of the compost, promotes the reproduction of microorganisms and the increase of nutrient content during the cooling stage, the maturation stage and the like. And the cation exchange capacity in the compost reflects the nutrient capacity, inorganic salt buffering performance of the biomass oil sludge pyrolysis residue rich in enzymes. It is effectively proved that the biomass oil sludge pyrolysis residue rich in enzymes has application potential as an organic fertilizer.

[0071] Further, the three-dimensional fluorescence (EEM) spectrum test is carried out on the compost B group of example 1. The three-dimensional fluorescence region is mainly divided into five regions: region I is tyrosine protein (Ex: 200~250 nm, Em: 280~330 nm), region II is tryptophan protein (Ex: 200~250 nm, Em: 330~380 nm), region III is fulvic acid protein (Ex: 200~250 nm, Em: 380~550 nm), region IV is soluble microbial metabolites (Ex: 200~250 nm, Em: 330~380 nm), and region V is humic acid humus (Ex: 200~250 nm, Em: 380~550 nm). The results are as shown in Figure 9As shown, it can be observed that the main substance in the compost B group is the protein (V) and humus of humic acid, which proves that the biomass of the oil sludge pyrolysis residue is successfully achieved in the compost B group. The key reason for this result is that the pig manure derives more microorganisms to convert the biomass into the protein (V) and humus of humic acid; and the hydrophobicity of the oil sludge pyrolysis residue improves the porosity of the pile, increases the porosity, increases the entry of the external air into the pile, increases the respiration of the microorganisms, accelerates the composting process, and leads to more organic matter to be converted into the protein (V) and humus of humic acid.

[0072] 3. Plant growth Test method: The growth of energy plants - Arundo donax and landscape plants - Medicago sativa and Festuca arundinacea is used to evaluate the soil improvement effect. The growth of plants in natural soil, residue contaminated soil (residue addition amount 5 wt%), different types of compost (compost B and compost E, addition amount 5 wt%) and different addition ratios (compost B addition amount 1 wt%, 2.5 wt% and 5 wt%) is explored. The garden landscape soil of Tianjin University Beiyang Garden Campus at No. 135 Yaguang Road, Jinnan District, Tianjin is used as the research object. The weight of the soil culture medium is 500 g, and the biomass of the oil sludge pyrolysis residue rich in enzymes is added in an amount of 1.0 wt%, 2.5 wt% and 5.0 wt% of the weight of the soil culture medium, respectively, and uniformly mixed for standby. The maximum water holding capacity of 500 g of soil is calculated to be 300 mL to ensure the required water for plant growth in the soil, and the soil is ploughed before the water is completely evaporated to ensure the respiration and water flow of the soil. Arundo donax is planted by cutting, the length of the Arundo donax seedlings is unified, and 3 plants are planted in each culture medium; Festuca arundinacea and Medicago sativa are planted by seed planting, and 60 seeds are planted in the soil layer 1-2 cm after the area is divided. The soil culture medium is irrigated by spraying at a rate of 100 mL / day, and the plants are harvested after 4 weeks of planting. The weight, root length, stem height, fresh weight and dry weight of Arundo donax, and the germination rate, stem and root height, survival rate and total weight (fresh and dry weight) of Festuca arundinacea and Medicago sativa are counted.

[0073] After the biomass of the oil sludge pyrolysis residue rich in enzymes obtained in Example 1 is evaluated in "2. Application potential", it is found to have organic fertilizer potential and is suitable for cultivating plants as an organic fertilizer. Therefore, in this part, the present inventors have done plant experiments to verify this result.

[0074] Figure 10 a and Figure 10In d, the height and growth rate of reed in natural soil (NS) were 45.3 cm and 181.2%, respectively, while the height and growth rate of reed in residue-contaminated soil (NS+R) were 25.4 cm and 101.6%, respectively. The comparison results showed that the natural soil had a certain potential to supply the growth of reed, while the oil sludge pyrolysis residue directly into the soil would destroy the soil structure and inhibit the growth of reed; this conclusion was consistent with the physicochemical properties of oil sludge pyrolysis residue. The groups of adding compost B in natural soil showed different promoting effects, which optimized the soil structure. The growth height and growth rate under NS+B1 (adding 1.0 wt% of compost B), NS+B2 (adding 2.5 wt% of compost B), and NS+B3 (adding 5.0 wt% of compost B) were 47.4 cm and 189.6%, 61.4 cm and 245.6%, and 49.8 cm and 199.2%, respectively. The difference in results showed that different addition ratios of compost B had different effects on soil improvement and plant growth promotion. The addition of 5 wt% of compost B could maximize the promotion of the absorption of organic matter in the soil by plants, while excessive organic fertilizer would not only cause waste of resources, but also promote the development of soil structure. This shows that the biomass-enzymatic oil sludge pyrolysis residue provided by the application has been proved to have application potential and can be used as an organic fertilizer for plant growth.

[0075] Figure 10 b、 Figure 11 e、 Figure 10 c、 Figure 11 f respectively shows the growth of alfalfa and tall fescue plants cultivated with seeds. The growth of alfalfa and tall fescue shows the same change trend as reed, that is, the addition of oil sludge pyrolysis residue inhibits soil activity, leading to a worse trend of plant growth. Further, the plant growth index after adding oil sludge pyrolysis residue is increased by 2-5 times, further proving the positive improvement effect of the biomass-enzymatic oil sludge pyrolysis residue provided by the application on soil activity. However, compared with reed, the changes and improved trends of alfalfa and tall fescue are more significant, which is closely related to the stress resistance and tolerance of the plants themselves. Alfalfa and tall fescue belong to leguminous plants, and the rhizobia produced by their root systems can fix nitrogen and improve the soil environment, and absorb more nutrients, which in turn promotes their own growth.

[0076] Figure 11 h and Figure 11i The main composition changes of Arundo donax, including crude fat, Arundo donax, lignocellulose ratio, in natural soil (NS), residue contaminated soil (NS+R), and soil added with 2.5 wt% of compost B (NS+B) growth environment. The highest lipid, chlorophyll a, and chlorophyll b in NS+B culture can reach 2.54%, 0.97 mg / g, and 0.81 mg / g. The main role of lipid in Arundo donax is to store energy, constitute biological membranes, and enhance signal transduction. At the same time, high content of lipid can improve the plant's response to soil adversity, such as salinization, drought, and temperature, etc. Arundo donax with high content of lipid also represents its potential as a functional raw material and energy plant. Chlorophyll is an indicator for evaluating plant photosynthesis and increasing its own organic matter content. The high content of chlorophyll a and chlorophyll b of Arundo donax in NS+B2 medium verifies its ability to absorb more CO2 to achieve carbon neutralization, and to convert into organic nutrients to supply its own growth. The highest content of cellulose and lignin in Arundo donax in NS+R and hemicellulose in Arundo donax in NS+B is 39.92 wt%, 17.95 wt%, and 39.29 wt%, respectively. Cellulose, as an important raw material for fuel ethanol, can also be prepared into tar for green energy through pyrolysis.

[0077] 4. Soil characteristics On the basis of "3. Plant growth", further test and analysis of the physical structure, chemical properties, and nutrient content of the soil before and after planting the plants. Figure 12 a shows the overall growth trend of Arundo donax, alfalfa, and tall fescue in natural soil, residue contaminated soil, and 2.5 wt% compost B improved substrate. It can be observed that natural soil has certain growth potential, while oil sludge pyrolysis residue directly into soil shows negative effect, showing the harm of oil sludge pyrolysis residue directly into soil. Therefore, it is necessary to carry out biomass treatment on oil sludge pyrolysis residue.

[0078] Figure 12 and Figure 13 The physicochemical properties of natural soil, natural soil + oil sludge pyrolysis residue, natural soil + 2.5 wt% compost B, and natural soil, natural soil + 2.5 wt% compost B after planting Arundo donax (NS+B1), alfalfa (NS+B2), and tall fescue (NS+B3) are shown.

[0079] Figure 12bThe bulk density of different stages of soil is shown. The effect of oil sludge pyrolysis residue on the bulk density of soil is small, while the bulk density of natural soil is significantly reduced by adding compost B. This may be due to the fact that compost B has a loose and porous structure, which optimizes the physical structure of the soil and promotes the loose and porous structure of the soil. The change in soil bulk density after planting shows obvious differences. The bulk density of natural soil after planting Phragmites australis has a significant rebound, which is due to the deposition of water and the growth of roots during plant growth, which leads to an increase in bulk density. The bulk density of soil after adding compost B and planting Phragmites australis, Medicago sativa, and Festuca arundinacea remains at a low level. The reason may be that the addition of compost B releases organic matter and increases the species and abundance of microorganisms in the improved soil, and promotes the growth of plants. The addition of compost B increases the overall organic matter content of the soil, resulting in a low bulk density of the soil, which still has high utilization value. The water held by the soil includes two parts: water held by the molecular attraction of soil particles and water held by the capillary attraction in soil pores. The water holding capacity mainly affects the physical properties of the soil, mainly affecting the dissolution, transfer, and microbial activity of nutrients in the soil, and ultimately affecting the soil fertility.

[0080] As Figure 12 The water holding capacity of NS, NS+R, and NS+B before planting is 22.5 g / kg, 21.9 g / kg, and 24.2 g / kg, respectively, as shown in c. The water holding capacity of natural soil and compost B improved soil after planting Phragmites australis, Medicago sativa, and Festuca arundinacea is 22.5 g / kg, 23.1 g / kg, 22.6 g / kg, and 22.8 g / kg, respectively. The water holding capacity of natural soil before and after planting remains the same, which may be the result of the combined action of various factors such as salt, organic matter, particles, bulk density, and other factors in the soil. The water holding capacity of the soil after adding compost B increases significantly, which indicates that the organic matter content of the compost improves the organic matter and mineral composition, increases the hydrophilicity of the soil particles, attracts more water molecules, and increases the water holding capacity. Compared with the water holding capacity of the soil before planting after adding compost B, the water holding capacity of the soil after planting decreases to varying degrees. The decrease in water holding capacity after planting may be due to the decrease in soil density and the deposition of water downward after planting. On the other hand, the content of organic matter in the soil decreases after supplying plants for growth, and the physical structure changes at different levels, resulting in a decrease in the water holding capacity of the soil. Cation exchange capacity (CEC) is an important indicator for evaluating soil fertility and buffer performance, and is also an important basis for improving soil and rational fertilization.

[0081] Figure 12dThe cation exchange capacity of different soils before and after planting was used to evaluate the effect of soil improvement. The cation exchange capacity of natural soil (NS), natural soil + oil sludge pyrolysis residue (NS+R), and natural soil + compost B (NS+B) was 18.2 cmol / g, 17.3 cmol / g, and 18.6 cmol / g, respectively. The results showed that the cation exchange capacity of the soil decreased significantly after the addition of oil sludge, while the cation exchange capacity of the soil increased after the addition of compost B. The decrease in cation exchange capacity may be due to the destruction of ion balance and the increase in soil salinization caused by the addition of carbonate and inorganic salt ions in the oil sludge residue. The addition of compost B, which contains a large amount of negative charges and anions, can promote ion exchange in the soil and release organic matter to promote plant growth. The cation exchange capacity of the soil after planting Phragmites australis, Medicago sativa, and Festuca arundinacea + compost B was 17.5 cmol / g, 17.9 cmol / g, 17.8 cmol / g, and 17.9 cmol / g, respectively. Compared with before planting, the cation exchange capacity of the soil decreased to different degrees, but was higher than that of the natural soil after planting. During plant growth, a large amount of positively charged nutrient ions (such as calcium, magnesium, potassium, and sodium) were consumed to support plant growth. The organic matter particles in the compost also have negative charges, which can attract positively charged cations to improve the soil. Effective nitrogen, phosphorus, and potassium are essential elements for plant growth and can change the elemental content and pH of the soil, affecting the community structure of microorganisms.

[0082] As shown in Figure 12 e, the nitrogen, phosphorus, and potassium content of the oil sludge residue was extremely low, and even had a negative impact on the original soil. The addition of compost B increased the nitrogen, phosphorus, and potassium content of the soil to 155.0 mg / kg, 77.6 mg / kg, and 597.0 mg / kg, respectively, further demonstrating the maturity and improvement effect of compost B. The microbial degradation during composting promotes the conversion of more raw materials into available substances. The nitrogen, phosphorus, and potassium content of the soil after planting Phragmites australis, Medicago sativa, and Festuca arundinacea decreased to different degrees, mainly due to the consumption during plant growth and normal microbial activity.

[0083] The content of soil organic matter is an important indicator for evaluating its quality, as Figure 12As shown in f, the soil organic matter (SOM) contents in NS, NS+B, NS+B1, NS+B2, and NS+B3 were 168.0 g / kg, 237.0 g / kg, 21.2 g / kg, 21.1 g / kg, and 21.9 g / kg, respectively. The data trends clearly demonstrate that compost B significantly increased the organic matter content in the soil and had a significant positive effect on soil improvement.

[0084] To investigate the soil amendment effect, the activities and types of enzymes in the soil were further measured, mainly including four types: S-UE, S-CAT, S-SC, and S-ACP. The results are as follows: Figure 13 As shown in g and 13h. The variation trend of S-UE is quite unique. The addition of compost B significantly increased its content, and the content of Reed, Alfalfa, and Tall Fescue was further increased after planting. This may be because the abundance and variety of microbial communities during plant growth increased, and the secreted substances increased the activity of S-UE enzymes. The contents of S-CAT, S-SC, and S-AC enzymes showed similar variation trends. Compared with natural soil, the enzyme content in the soil increased after adding compost B, but the enzyme activity decreased to varying degrees after planting. This result indicates that the enzyme-rich biomass pyrolysis residue of oil sludge provided by this invention is not only rich in a variety of enzymes, but also maintains or even exceeds its enzyme activity after planting.

[0085] 5. Soil activity Microbial community analysis is crucial for evaluating soil activity. It has been reported that the trends in the types and quantities of soil microorganisms before and after improvement are important indicators for evaluating soil properties. This section selected the original soil sample (A1), the soil sample with the addition of 2.5 wt% compost B (A2), and the soil sample after the completion of Reed sphagnum moss planting (A3, where the soil sample had 2.5 wt% compost B added) to evaluate the impact of the enzyme-rich biomass-based oil sludge pyrolysis residue provided in this invention on the microbial community.

[0086] observe Figure 14 and Figure 15It can be seen that 20 kinds of bacteria and 20 kinds of fungi were detected in the soil. Among them, Acidobacteria bacterium (Lactobacillus), Actinobacteria bacterium (Actinomycete), Chloroflexi bacterium (Chloroflexi), Betaproteobacteria bacterium (Beta-proteobacteria), Deltaproteobacteria bacterium (Delta-proteobacteria), and Gemmatimonadetes bacterium (Gemmatimonadetes) occupy a dominant position. Notably, these six bacteria showed a gradually decreasing trend in the original soil, the improved soil, and the planted soil, respectively. The intensity of microorganisms in A2 soil was the highest relative to A1 and A3, which proved that the soil improvement substrate effectively increased the abundance of microbial communities in the soil. The soil improvement substrate is rich in various enzymes, and it is speculated that the increase in microbial community abundance is positively correlated with high enzyme content, which is crucial for plant growth. The Actinophytocolaalgeriensis genus showed a significant growth trend after the addition of enzyme-rich biomassized-oil-slime pyrolysis residues, which also proved the decomposition of organic matter during the composting process, promoting the release of more nutrients in the soil for plant growth. The Acidobacteria bacterium genus also showed a significant growth trend after the addition of enzyme-rich biomassized-oil-slime pyrolysis residues, which proved that the emission of NH3 during the organic composting process led to the growth of acid bacillus microorganisms, the overall pH value decreased, and had the effect of reducing soil alkalinity. Among the fungal genera, Alternaria, Chaatomium, Fusarium, and Aspergillus accounted for a high proportion, all exceeding 5%. However, Alternaria showed a significant increase after the addition of organic fertilizer, even accounting for more than 20%, the reason may be due to the humification during the composting process, which promotes the decomposition of organic matter, but the excessive proportion may affect the healthy growth of plants. Interestingly, the Rhizopus genus showed a significant increase after the addition of enzyme-rich biomassized-oil-slime pyrolysis residues, playing a positive role. The role of Rhizopus mainly focuses on improving soil structure, improving fertility, decomposing organic waste, further promoting material circulation and waste utilization, achieving soil improvement and plant growth.

[0087] Figure 16 Differential analysis of KEGG metabolic pathways is given. The increase in microbial abundance in the soil improved by enzyme-rich biomassized-oil-slime pyrolysis residues indicates an increase in the number of genes involved in metabolism or biosynthesis, an increase in nitrogen cycling and nutrients in the soil, which is more conducive to the growth of energy plants.

[0088] Figure 17 The results of EggNOG showed that the function unknown, energy production and conversion, amino acid transport and metabolism functional groups occupied the main position, mainly acting on the release of nutrients, energy production and conversion and metabolic effects of plant growth process. Figure 18 and Figure 19 The microbial species abundance change trend chart is shown, and the abundance of microorganisms in the three stages of soil shows a significant normal change trend. The soil modified by the enzyme-rich biomassized oil sludge pyrolysis residue increases from 1661 to 1974 compared with the original soil, because the enzyme-rich biomassized oil sludge pyrolysis residue increases the types of microorganisms in the soil and improves the abundance of microorganisms in the soil. The reason for the decrease in the types of microorganisms in the soil after planting may be that after the completion of planting, the nutrients and water in the soil have been consumed, and it is difficult to supply the survival of microorganisms, resulting in death. Overall, the addition of enzyme-rich biomassized oil sludge pyrolysis residue significantly optimizes the types and abundance of microorganisms in the soil, which is beneficial to the decomposition and conversion of nutrients, organic matter, nitrogen elements and other nutrients in the soil to supply the growth of plants; this result is highly related to the S-UE, S-ACP, S-CAP and S-SC contained in the enzyme-rich biomassized oil sludge pyrolysis residue.

Claims

1. A process for the preparation of an enzyme-rich biomass oil slurry pyrolysis residue, characterized by, The application relates to a method for preparing an enzyme-rich biomass-oil sludge pyrolysis residue. The initial carbon-nitrogen ratio of the compost raw material is (24-26):

1.

2. The production method according to claim 1, wherein The biomass is at least one of corn straw, fallen leaves, rice husks and peanut shells.

3. The production method according to claim 1 or 2, characterized by, The particle size of the biomass is 20-40 mesh.

4. The production method according to claim 1, wherein The livestock and poultry manure is at least one of pig manure, sheep manure, chicken manure, duck manure and cow manure.

5. The production method according to claim 1 or 2 or 4, characterized by, The mass ratio of the oil sludge pyrolysis residue, the biomass and the livestock and poultry manure is (10-14):1:

3.

6. The production method according to claim 1, wherein The composting treatment time is 4-5 weeks.

7. The enzyme-enriched biomass pyrolysis residue obtained by the preparation method according to any one of claims 1-6, characterized in that, The enzyme-rich biomass-oil sludge pyrolysis residue has a pore structure.

8. The enzyme-rich biomass slurry char pyrolysis residue of claim 7, wherein, In the enzyme-rich biomass-oil sludge pyrolysis residue, the urease content is 9000-10000 mu / d / g, and the sucrase content is 135-145 mmol / d / g.

9. A substrate for soil greening, characterized by, The application further relates to a soil substrate containing the enzyme-rich biomass-oil sludge pyrolysis residue.

10. Use of the substrate for soil greening according to claim 9 for growing energy plants, characterized in that, The energy plant is Arundo donax, Medicago sativa or Festuca arundinacea.

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