CN113293004A - Oil sludge pyrolytic carbon-based soil conditioner and preparation method thereof - Google Patents
Oil sludge pyrolytic carbon-based soil conditioner and preparation method thereof Download PDFInfo
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Abstract
An oil sludge pyrolytic carbon-based soil conditioner and a preparation method thereof. The oil sludge pyrolytic carbon-based soil conditioner comprises the following components in parts by weight: 50-65 parts of oil field ground oil sludge thermal cracking product carbon, 10-20 parts of lignin, 3-5 parts of sodium alginate, 1-2 parts of polyvinyl alcohol, 3-5 parts of beneficial microbial inoculum and 2-5 parts of alkaline fertilizer. The oil field falls to ground fatlute anaerobic thermal cracking carbonaceous in this application is the carbon back, cooperates alkaline fertilizer and beneficial bacterium preparation carbon back alkaline soil amendment, has solved the solid product carbonaceous's that the oil field falls to ground fatlute pyrolysis treatment after the problem of going out of way, has realized the utilization of oil-containing sludge resources.
Description
The technical field is as follows:
the invention relates to the technical field of harmless and recycling of oil field solid wastes, in particular to an oil sludge pyrolytic carbon-based soil conditioner and a preparation method thereof.
Background art:
the oil-containing pollutants come from waste drilling fluid, fracturing flowback fluid, oil sludge at the bottom of an oil gathering and transportation and refining tank, oil sludge at the bottom of a pit in an oil-gas field development field, oil sludge on the ground and the like. The oil sludge falling to the ground is an oil-containing solid waste generated in the production or storage and transportation process of the oil field ground, the composition is complex, light components in oil volatilize, heavy components of asphaltene and colloid are increased, and the treatment is difficult. The oil field oil sludge treatment method solves the treatment problem of products after oil field oil sludge treatment, and generally the oil sludge treatment is less and has low heavy metal content. The product is mainly carbon, and the heavy metal is little, so that the carbon is relatively excellent in quality.
The soil surface layer is poor in structure due to lack of organic matters, the structure is damaged and the soil is dispersed under the action of irrigation, rainfall and other external factors, and the soil surface is hardened under the action of cohesive force after drying, so that the soil is hardened. The yield of crops planted on the hardened soil is very low.
The invention content is as follows:
the invention aims to provide an oil sludge pyrolytic carbon-based soil conditioner and a preparation method thereof, which solve the problem of carbon in a solid product after pyrolysis treatment of oil field ground oil sludge and realize resource utilization of oil-containing sludge; improve soil and provide excellent growth conditions for planting crops.
The technical scheme of the invention is as follows: the oil sludge pyrolytic carbon-based soil conditioner comprises the following components in parts by weight: 50-65 parts of oil field ground oil sludge thermal cracking product carbon, 10-20 parts of lignin, 3-5 parts of sodium alginate, 1-2 parts of polyvinyl alcohol, 3-5 parts of beneficial microbial inoculum and 2-5 parts of alkaline fertilizer.
65 parts of carbon of a thermal cracking product of the ground oil sludge in the scheme, 20 parts of lignin, 5 parts of sodium alginate, 4 parts of a fertilizer, 3 parts of a beneficial microbial inoculum and 2 parts of polyvinyl alcohol.
The alkaline fertilizer is any one or a combination of more of calcium superphosphate, dicalcium silicate, calcium magnesium silicate, sodium metasilicate, ferrous sulfate and zinc sulfate. The average carbon content of the thermal cracking product of the oil field ground oil sludge is 40-60%. The average particle size of the oil sludge pyrolytic carbon-based soil conditioner is 2-6 mm.
The preparation method of the oil sludge pyrolytic carbon-based soil conditioner comprises the following steps:
step 1, using ground oil sludge as a raw material, adopting smoke to heat and continuously operate a high-temperature rotary kiln, controlling the temperature to be more than 550 ℃, sealing and isolating oxygen, simultaneously adopting nitrogen protection under micro-positive pressure, and staying for 8 hours to prepare the thermal cracking product carbon of the ground oil sludge of the oil field, wherein the carbon content is 40-60%, and the heavy metal content can meet the index standard requirement specified in agricultural sludge pollutant control standard (GB 4284-1984));
step 2, preparing beneficial microbial inoculum:
respectively adding 5 strains to be expanded, photosynthetic bacteria, filamentous bacteria of fermentation system, gram-positive actinomycete group, yeast bacteria and lactic acid bacteria into 500L seed tank, wherein 450L culture medium and 25L bacteria liquid are filled in 500L seed tank, and the bacteria content in each ml of the bacteria liquid reaches 109Preparing culture medium from corn flour, soybean flour, white granulated sugar, yeast extract, trace nutrient elements potassium dihydrogen phosphate and magnesium sulfate, sterilizing at 120 deg.C under 0.1Mpa for 30 min; adding strain, maintaining at 30-40 deg.C for 24 hr, ventilating the seeding tank with screw air compressor to increase oxygen demand of microorganism, sterilizing with steam at 120 deg.C and 0.1Mpa for 30min in the air system, opening the vent valve of the seeding tank to control air flow, gradually increasing and decreasing the ventilation process, maintaining the pressure of the seeding tank at 0.04Mpa and temperature at 30-40 deg.C, sampling every 2 hr after 24 hr, sampling with steam at 120 deg.C and pressure at 0.1Mpa before sampling,sterilizing for 30min, collecting 2 groups of samples each time, detecting, storing, observing growth state of microorganism strain until the number of microorganisms in the fermentation solution reaches 109Transferring the fermentation liquid in 500L seed tank to three 1500L fermentation tanks for culture, wherein the 1500L fermentation tanks are filled with 1200L culture medium, steam 120 deg.C is required to be applied to the transfer pipeline before the seed transfer process, the pressure is 0.1Mpa, the sterilization is maintained for 30min, the 1500L fermentation tank is the same as the seed tank in expanding culture, sampling is performed every 2 hours after 48 hours, steam 120 deg.C and 0.1Mpa are required to be applied to the samples before sampling, the sterilization is maintained for 30min, 3 groups of samples are detected and filed every time, the microbial activity and growth state are observed, and the bacterial content in the fermentation liquid reaches 109After each ml, purifying by a plate-and-frame filter press, and culturing 5 strains according to the same method to obtain a dry powder microbial inoculum;
step 3, preparing a sodium alginate glue solution, namely adding water into sodium alginate to prepare a sodium alginate solution, wherein the mass concentration of the sodium alginate solution is 5-10%, and then sequentially adding oil sludge thermal cracking product carbon, lignin and polyvinyl alcohol into the sodium alginate glue solution to be uniformly mixed to obtain a first mixed glue solution;
step 4, mixing the five dry powder inoculants prepared in the step 2 according to a mass ratio of 1: 1: 1: 1: 1 proportion, diluting with water to obtain bacterial suspension, wherein the mass concentration of the bacterial suspension is 1-3%, and adding alkaline fertilizer to mix to obtain a second mixed glue solution.
Step 5, mixing the step 3 and the step 4 according to the mass ratio of 3: 1, and carrying out a crosslinking reaction to obtain the oil sludge pyrolytic carbon-based soil conditioner.
The lignin in the scheme is obtained by separating and drying the straw fermentation product, can be slowly degraded by microorganisms in soil and converted into humus, and has a certain inhibiting effect on the activity of soil urease, so that the decomposition of urea nitrogen is further delayed, and the absorption and utilization of nitrogen by crops are promoted; meanwhile, active groups such as hydroxyl, carboxyl, phenolic hydroxyl and the like in lignin molecules have strong adsorbability and complexation, so that the network structure of the lignin has huge adsorbability, and can adsorb excessive nitrogen generated by hydrolysis and cannot be absorbed and utilized by crops, thereby delaying the decomposition of urea nitrogen in the fertilizer and achieving the slow release effect. In addition, the lignin can chelate Ca, S, Fe, Cu, Zn, Mn and other elements in the soil, kill harmful bacteria and viruses in the soil, inhibit the growth of root-knot nematodes, resist diseases and continuous cropping and reduce pesticide residue. Therefore, lignin is added into the carbon-based fertilizer, so that the waste of the lignin is avoided, and the fertilizer efficiency of the carbon-based fertilizer can be obviously improved.
The sodium alginate and the polyvinyl alcohol in the scheme are blended to form the hydrogel sodium alginate-polyvinyl alcohol, the hydrogel sodium alginate-polyvinyl alcohol has good film forming property, chemical stability and biocompatibility, and can be wrapped on the surfaces of fertilizers and beneficial bacteria so as to generate a slow release effect, the molecular weight of the sodium alginate is 150000-300000, the cross-linking effect is mainly achieved, and the molecular weight of the polyvinyl alcohol is 5000-8000 low-polymerization-degree vinyl alcohol, and the embedding effect is achieved. In addition, sodium alginate is also a natural soil conditioner, can promote the formation of a soil granular structure, improve the internal pore space of soil, coordinate the proportion of solid, liquid and gas in the soil, recover the natural colloid balance of the soil lost due to overload or chemical pollution, increase the biological activity of the soil, promote the release of available nutrients, facilitate the growth of root systems and improve the stress resistance of crops.
The alkaline fertilizer in the scheme contains a plurality of salt-based ions, such as calcium, magnesium, zinc and the like, and the salt-based ions can reduce the content of hydrogen ions and alternating aluminum ions in the soil and also can increase the content of mineral nutrients in the soil.
Five floras in the beneficial microbial inoculum in the scheme are as follows:
1. photosynthetic bacteria group: prokaryotes with a light energy synthesis system are gram-negative bacteria without the capability of forming spores, light and heat received by soil are taken as energy sources, organic matters of root systems or harmful gas (hydrogen sulfide) ammonia and the like are taken as hydrogen donor and carbon source to carry out photosynthesis to generate metabolites such as amino acid, nucleic acid and the like, and the metabolites can be directly absorbed by plants and can also be taken as substrates for other microorganism propagation activities to improve the nitrogen fixation capability of the plants. It also has effects in promoting growth of animal and plant, improving disease resistance, and promoting life activity and growth of animal and plant.
2. Filamentous fungi of fermentation system: mainly Aspergillus used in alcohol fermentation, which can coexist with other microorganisms and has a good effect on the formation of esters in soil. Because the alcohol generating ability is strong, it can prevent maggots and other vermin and eliminate offensive odor.
3. Gram-positive actinomycete group: actinomycetes are a group of prokaryotes which grow mainly in the shape of hyphae and reproduce in spores and have strong terrestrial property. Gram-positive, is an important producer of some bioactive substances such as antibiotics and the like, and has an important role in the biological control of crop pests and diseases. Can also synthesize various useful metabolites such as amylase, cellulase, amino acid, vitamin and the like. Promoting the soil to form a granular structure in the soil so as to improve the soil.
4. And (3) yeast flora: the yeast is unicellular fungus, aerobe and important nutrition functional bacteria, and can reasonably convert and efficiently absorb available nutrients in various substrate environments such as soil, water and the like; also has fermentation and decomposition effects, and can form various B vitamins and physiologically active substances in growth and metabolism to enhance the activity of effective bacteria.
5. The lactic acid bacteria group: the main product of the lactobacillus fermentation saccharides is lactic acid, which is a general name of a spore-free gram-positive bacterium. Is a prokaryote. The sugar is used for aerobic respiration under aerobic condition, energy is obtained in the process of sugar decomposition, cell substances are synthesized, and lactic acid is generated in an anoxic environment to inhibit the growth of spoilage microorganisms in a growth environment. Lactic acid has strong bactericidal power, and can effectively inhibit the activity of harmful microorganisms and the rapid putrefaction and decomposition of organic matters. The lactobacillus can also effectively inhibit the proliferation of pathogenic bacteria caused by continuous cropping obstacles.
In a word, the beneficial microbial inoculum can improve soil fertility, purify the environment, promote the growth and development of animals and plants, obviously increase the yield and prevent diseases, enhance the resistance of the animals and plants, and promote early germination, early flowering and early maturity of crops.
The invention has the following beneficial effects:
the invention adopts the carbon of the anaerobic thermal cracking product of the fallen oil sludge as the raw material, the carbon has the most typical characteristics of porous structure and large specific surface area, the carbon is used as the raw material of the carbon-based fertilizer, the water retention, fertilizer retention and buffer capacity of the matrix are greatly increased, the matrix subjected to high-temperature carbonization does not contain any mixed bacteria, and the plant diseases and insect pests are greatly reduced.
The soil conditioner can provide abundant carbon sources for microorganisms in soil, stimulate the activity of soil microorganisms, and promote the decomposition of the soil microorganisms on organic substances, so that the soil fertility is improved. After the biochar is applied to soil, the acid-base balance of the soil is maintained, the accumulation of the content of available nutrients in the soil is promoted, the content of organic matters in the soil is increased, the growth environment of plant root systems is improved, the utilization rate of fertilizers is increased, water and soil pollution and nutrient loss are reduced, and the soil improvement effect is promoted. The biochar is slowly decomposed in the soil, and long-term application of the biochar has a promoting effect on soil carbon accumulation.
Description of the drawings:
FIG. 1 is a schematic structural view of the present invention;
the specific implementation mode is as follows:
the invention is further illustrated by the following examples:
examples 1,
The soil conditioner comprises the following raw materials, by weight, 65 parts of a thermal cracking product (with a carbon content of 40-60%) of ground oil sludge, 20 parts of lignin, 5 parts of sodium alginate, 5 parts of calcium superphosphate, 2 parts of polyvinyl alcohol and 3 parts of a beneficial microbial inoculum.
The preparation method comprises the following steps:
step 1, preparing a sodium alginate solution: adding water into sodium alginate to prepare a sodium alginate solution with the mass concentration of 10%.
Step 2, preparing a first mixed glue solution: and (3) uniformly mixing the lignin, the polyvinyl alcohol and the thermal cracking product of the oil sludge falling to the ground with the sodium alginate solution prepared in the step (1) to obtain a first mixed glue solution.
Step 3, preparing a second mixed glue solution: diluting the beneficial microbial inoculum with water to prepare a bacterial suspension with the mass concentration of 3%, and adding calcium superphosphate to mix to obtain a second mixed glue solution;
step 4, crosslinking reaction: mixing the first mixed glue solution and the second mixed glue solution according to the mass ratio of 3: 1 proportion, and carrying out a crosslinking reaction to obtain the carbon-based soil conditioner. The average grain diameter of the carbon-based soil conditioner is 6 mm.
Examples 2,
The soil conditioner comprises the following raw materials, by weight, 55 parts of a thermal cracking product (with a carbon content of 40-60%) of ground oil sludge, 15 parts of lignin, 4 parts of sodium alginate, 3 parts of dicalcium silicate, 2 parts of polyvinyl alcohol and 3 parts of a beneficial microbial inoculum.
The preparation method comprises the following steps:
step 1, preparing a sodium alginate solution: adding water into sodium alginate to prepare a sodium alginate solution with the mass concentration of 5%.
Step 2, preparing a first mixed glue solution: and (3) uniformly mixing the lignin, the polyvinyl alcohol and the thermal cracking product of the oil sludge falling to the ground with the sodium alginate solution prepared in the step (1) to obtain a first mixed glue solution.
Step 3, preparing a second mixed glue solution: diluting the beneficial microbial inoculum with water to prepare a bacterial suspension with the mass concentration of 1%, and adding dicalcium silicate to mix to obtain a second mixed glue solution.
Step 4, crosslinking reaction: and (3) mixing the first mixed glue solution and the second mixed glue solution according to a mass ratio of 3: 1 proportion, and carrying out a crosslinking reaction to obtain the carbon-based soil conditioner. The average grain diameter of the carbon-based soil conditioner is 2 mm.
Examples 3,
The soil conditioner comprises, by weight, 50 parts of a thermal cracking product of the ground oil sludge (the carbon content is 40-60%), 10 parts of lignin, 3 parts of sodium alginate, 2 parts of zinc sulfate, 1 part of polyvinyl alcohol and 5 parts of a beneficial microbial inoculum.
The preparation method comprises the following steps:
step 1, preparing a sodium alginate solution: adding water into sodium alginate to prepare a sodium alginate solution with the mass concentration of 8%.
Step 2, preparing a first mixed glue solution: and (3) uniformly mixing the lignin, the polyvinyl alcohol and the thermal cracking product of the oil sludge falling to the ground with the sodium alginate solution prepared in the step (1) to obtain a first mixed glue solution.
Step 3, preparing a second mixed glue solution: diluting the beneficial microbial inoculum with water to prepare bacterial suspension with the mass concentration of 2%, and adding zinc sulfate to mix to obtain a second mixed glue solution.
Step 4, crosslinking reaction: and (3) mixing the first mixed glue solution and the second mixed glue solution according to a mass ratio of 3: 1 proportion, and carrying out a crosslinking reaction to obtain the carbon-based soil conditioner. The average grain diameter of the carbon-based soil conditioner is 4 mm.
Experiment I, saline-alkali soil is selected for improvement, and a soil improvement area of 100m is designed2Control group 100m2Each treatment is repeated for 3 times, and the conditioner prepared in example 1 is uniformly applied to the soil surface of a soil improvement area in 5 months in 2018 at one time, and the dosage is 100m2The adding amount is 10kg, and a rotary cultivator is used for uniformly turning into the plough layer for 0-20 cm. The irrigation mode in the growth period is underground water under-film drip irrigation. Compared with the test area and the control area, the PH value of the soil is reduced to 7.49 after the planting in 2018, the volume weight of the soil can be reduced by adding the active carbon, the permeability of the soil is improved, the salt is lost under the action of rainwater and irrigation and leaching, and the salt content of the soil is reduced. The conductivity of the soil is reduced by 71.28%, the content of microorganisms in the soil is increased by 4.5 times within 0-20cm, and the yield of the tomatoes is increased by 31.63%.
Experiment II, collecting Cd-contaminated soil (the content of total Cd is 3.58mg/kg), adding a soil conditioner (example 2) with the mass concentration of 1% into 1kg of soil, fully and uniformly mixing, placing in a plastic basin (3 groups are parallel), adding water, sealing the plastic basin by using a preservative film and a rubber band, reserving holes, and keeping the field water holding capacity of the soil to be 80%. The plastic pots were incubated in a thermostatted incubator at 25 ℃ and weighed and moisturized once a week. And a blank control group was set. And 120d, results show that the addition of the modifying agent can improve the air permeability of the soil, stimulate the activity of soil microorganisms, increase the content of organic matters in the soil by 20% in a short time, and meanwhile, the application of the modifying agent is beneficial to the conversion of Cd in the soil from an oxidizable state to a reducible state and a residue state, so that the effectiveness of the Cd is reduced, and the anti-pollution capability of the soil is improved.
Claims (6)
1. The oil sludge pyrolytic carbon-based soil conditioner is characterized by comprising the following components in parts by weight: 50-65 parts of oil field ground oil sludge thermal cracking product carbon, 10-20 parts of lignin, 3-5 parts of sodium alginate, 1-2 parts of polyvinyl alcohol, 3-5 parts of beneficial microbial inoculum and 2-5 parts of alkaline fertilizer.
2. The oil sludge pyrolytic carbon-based soil conditioner according to claim 1, wherein the thermal cracking product of the fallen oil sludge comprises 65 parts of carbon, 20 parts of lignin, 5 parts of sodium alginate, 4 parts of fertilizer, 3 parts of beneficial microbial inoculum and 2 parts of polyvinyl alcohol.
3. The oil sludge pyrolytic carbon-based soil conditioner according to claim 1, wherein the alkaline fertilizer is any one or a combination of more of calcium superphosphate, dicalcium silicate, calcium magnesium silicate, sodium metasilicate, ferrous sulfate and zinc sulfate.
4. The oil sludge pyrolytic carbon-based soil conditioner according to claim 1, wherein the average carbon content of the thermal cracking product of the oil field ground oil sludge is 40-60%.
5. The oil sludge pyrolytic carbon-based soil conditioner according to claim 1, wherein the average particle size of the oil sludge pyrolytic carbon-based soil conditioner is 2-6 mm.
6. The preparation method of the sludge pyrolytic carbon-based soil conditioner according to any one of claims 1 to 5, characterized by comprising the following steps:
step 1, using the ground oil sludge as a raw material, heating by using flue gas, continuously operating a high-temperature rotary kiln, controlling the temperature to be above 550 ℃, sealing and isolating oxygen, simultaneously adopting nitrogen protection at micro-positive pressure, and staying for 8 hours to prepare the carbon of the thermal cracking product of the ground oil sludge of the oil field, wherein the carbon content is 40-60%;
step 2, preparing beneficial microbial inoculum:
adding 5 strains to be expanded, photosynthetic bacteria, filamentous bacteria of fermentation system, gram-positive actinomycete group, yeast bacteria and lactic acid bacteria to 500LIn the seeding tank, 500L seeding tank is filled with 450L culture medium and 25L flora solution, and the bacteria content in each ml of the flora solution reaches 109Preparing culture medium from corn flour, soybean flour, white granulated sugar, yeast extract, trace nutrient elements potassium dihydrogen phosphate and magnesium sulfate, sterilizing at 120 deg.C under 0.1Mpa for 30 min; adding strains, keeping the strains at the temperature of 30-40 ℃ for 24 hours, starting a screw air compressor to ventilate a seed tank, increasing the oxygen demand of microorganisms, adopting steam at the temperature of 120 ℃ and the pressure of 0.1Mpa in the early stage of an air system, keeping steam sterilization for 30 minutes, opening an exhaust valve of the seed tank to control the air volume, gradually increasing or decreasing the ventilation process, keeping the pressure of the seed tank at 0.04Mpa and the temperature at 30-40 ℃ after 24 hours, sampling every 2 hours, keeping the steam at 120 ℃ and the pressure at 0.1Mpa before sampling, keeping sterilization for 30 minutes, detecting and archiving 2 groups of samples every time, observing the growth state of the microbial strains, and ensuring that the number of microorganisms in the fermentation solution reaches 109Transferring the fermentation liquid in 500L seed tank to three 1500L fermentation tanks for culture, wherein the 1500L fermentation tanks are filled with 1200L culture medium, steam 120 deg.C is required to be applied to the transfer pipeline before the seed transfer process, the pressure is 0.1Mpa, the sterilization is maintained for 30min, the 1500L fermentation tank is the same as the seed tank in expanding culture, sampling is performed every 2 hours after 48 hours, steam 120 deg.C and 0.1Mpa are required to be applied to the samples before sampling, the sterilization is maintained for 30min, 3 groups of samples are detected and filed every time, the microbial activity and growth state are observed, and the bacterial content in the fermentation liquid reaches 109After each ml, purifying by a plate-and-frame filter press, and culturing 5 strains according to the same method to obtain a dry powder microbial inoculum;
step 3, preparing a sodium alginate glue solution, namely adding water into sodium alginate to prepare a sodium alginate solution, wherein the mass concentration of the sodium alginate solution is 5-10%, and then sequentially adding the thermal cracking products of oil sludge, namely carbon, lignin and polyvinyl alcohol into the sodium alginate glue solution to uniformly mix to obtain a first mixed glue solution;
step 4, mixing the five dry powder inoculants prepared in the step 2 according to a mass ratio of 1: 1: 1: 1: 1 proportion, diluting with water to obtain bacterial suspension, wherein the mass concentration of the bacterial suspension is 1-3%, and adding alkaline fertilizer to mix to obtain a second mixed glue solution.
Step 5, mixing the step 3 and the step 4 according to the mass ratio of 3: 1, and carrying out a crosslinking reaction to obtain the oil sludge pyrolytic carbon-based soil conditioner.
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