CN113699055B - Technical equipment for emulsifying and activating microbial inoculum - Google Patents
Technical equipment for emulsifying and activating microbial inoculum Download PDFInfo
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Abstract
The invention discloses technical equipment for microbial inoculum emulsification activation, which comprises a pyrolysis furnace, a feed inlet, a purge gas inlet, a pyrolysis gas discharge pipeline, a conveying facility, a cooling area and a discharge opening, wherein gas is circulated in a closed loop in the processes of feeding, pyrolysis, discharging, conveying and cooling. The process of forming the semi-coke is safe and environment-friendly, improves the resource utilization rate of plant source carbon sources, can remove organic pollutants in soil for a long time, and can be used for repairing the soil together with the composite bacterial liquid and the activating agent, thereby improving the activity of microorganisms and the soil repairing efficiency and increasing the soil fertility.
Description
Technical Field
The invention relates to the technical field of soil improvement and restoration, in particular to technical equipment and a method for improving soil by utilizing a composite microbial inoculum in a solidified form and activating the composite microbial inoculum.
Background
Soil organic pollution refers to pollutants composed of natural organic matters in the forms of carbohydrates, proteins, amino acids, fats and the like and certain other biodegradable synthetic organic matters. During the exploitation, storage, transportation and petrochemical production of petroleum, leakage events are often accompanied, and a large amount of petroleum enters soil to pollute the environment. Aromatic substances in petroleum pollutants have great toxicity to human beings and animals, and particularly aromatic hydrocarbons represented by polycyclic and tricyclic rings. The leakage of petroleum and petroleum products is one of the main sources of the toxic organic pollutants which are widely distributed and stably exist in natural environment and contain two or more benzene rings, and the toxic organic pollutants can enter human bodies or animal bodies through respiration, skin contact and diet intake modes, influence the normal functions of organs such as liver, kidney and the like, and even cause canceration. Some petroleum hydrocarbons, after entering animals, even have carcinogenic, teratogenic, mutagenic hazards to mammals and humans.
Petroleum substances enter the soil, so that the physicochemical properties of the soil can be changed, such as blocking soil pores, changing the composition and structure of soil organic matters, causing the change of carbon-nitrogen (C/N) and carbon-phosphorus ratio (C/P) of the soil organic matters, even destroying the original ratio of carbon, nitrogen and phosphorus in the soil, and causing the change of a soil microbial community and a microbial zone system. Organic pollution easily causes soil hardening, and the pH value is changed, so that the structure and the composition of the soil are destroyed, thereby bringing great negative influence to the ecological environment, crop production and human survival of the polluted area. Therefore, the repair and optimization of organically contaminated soil is an important task related to human survival.
The currently adopted repairing technologies mainly comprise a gas phase extraction method, a thermal desorption method, a chemical leaching method, an oxidation-reduction method, a biological repairing method and the like, and the repairing technologies for polluted sites such as polycyclic aromatic hydrocarbon and the like mainly comprise soil leaching, thermal desorption, chemical oxidation, biological repairing, phytoremediation and the like. However, the method has the problems of poor removal effect, high cost, easiness in causing secondary pollution, long time consumption and the like. Therefore, it is necessary to provide a soil restoration and improvement technique with good organic pollutant removal effect.
Disclosure of Invention
In order to overcome the problems, the invention has been studied and found: in the organic contaminated soil, the microbial inoculum is mainly adopted, solidified on semicoke carbon and properly emulsified and activated, and the obtained soil conditioner can safely and efficiently improve the soil contaminated by aromatic substances in petroleum, thereby completing the invention.
Specifically, the invention aims to provide a composite microbial inoculum in a solidified form, which is preferably subjected to emulsification activation to obtain a composite soil conditioner, and comprises the following components in parts by weight:
0.1 to 2 parts of microbial inoculum, preferably 0.5 to 1 part,
10 parts of biobased pyrolytic carbon.
In the invention, the microbial inoculum is a composite bacterial liquid formed by different strains, and the strains are two or more selected from trichoderma, saccharomycetes, bacillus megaterium, photosynthetic bacteria, halomonas, bacillus subtilis and pseudomonas aeruginosa.
According to the invention, the bacterial agent or bacterial liquid obtained as above is solidified on a bio-based solid material, preferably pyrolytic carbon or semicoke carbon, which is in the form of granules, preferably mixed with other inorganic granules. The mixing may be physical mixing of the semi-coke and the inorganic particulate material, each in the finished product, or in situ mixing during the preparation process.
According to the invention, the in situ mixing is accomplished in a pyrolysis apparatus comprising a pyrolysis furnace, a feed inlet, a purge gas inlet, a pyrolysis gas discharge line, a transfer means, a cool down zone and a discharge outlet. Preferably, the gas is circulated in a closed loop during the feeding, pyrolysis, discharging, conveying and cooling processes.
In the pyrolysis according to the invention, the vegetable carbon source is pyrolyzed in a pyrolysis apparatus, wherein the pyrolysis is carried out at a medium and low temperature in a pyrolysis furnace 1. Inert gas (such as nitrogen or carbon dioxide gas) is introduced to purge before pyrolysis, and the temperature of the pyrolysis furnace reaches 300-600 ℃.
Simultaneously with or after the addition of the vegetable carbon source, calcium oxide and/or calcium carbonate is added to the pyrolysis furnace before separating the semicoke carbon particles.
According to the invention, the carbocoal produced contains organic substances with higher boiling points and can be directly pressed into a certain shape, preferably with calcium carbonate. The semicoke is preferably crushed and then compression molded, such as in the form of microspheres, strips or rods, preferably with the pyrolysis oil obtained, which acts as a binder.
According to the invention, the load curing is carried out by means of dipping. Therefore, the semicoke carbon is soaked in bacterial liquid to obtain the semicoke carbon with biological activity.
According to the invention, an activator consisting of a solute and a solvent is added simultaneously or after soaking, the solvent is water, and the solute comprises a carbon source, a nitrogen source, a phosphorus source and trace elements, and preferably comprises trimethylammonioethylene lactone and nitrilotriacetic acid.
According to the invention, the mass ratio of the composite soil conditioner to the soil to be optimized to be tested is (2-8): 100, preferably (3 to 5): 100.
the invention has the beneficial effects that:
(1) The soil improvement technology provided by the invention has the advantages that the semi-coke forming process is safe and environment-friendly, secondary pollution is not caused, the resource utilization rate of plant source carbon sources is improved, and organic pollutants in soil can be removed for a long time;
(2) The soil conditioner provided by the invention has the advantages that the carbocoal and the compound bacteria liquid are jointly used for soil remediation, so that the activity of microorganisms is improved, the soil remediation efficiency is improved, and the soil fertility is improved;
(3) According to the soil improvement method provided by the invention, the activator with a proper proportion is added into the modifier, so that the degradation efficiency of organic pollutants is improved, the fertility of soil is improved, the steps are simple, the operation is convenient, the conditions are controllable, and the cost is lower.
Drawings
Fig. 1 is a schematic diagram of the apparatus of the present invention.
Detailed Description
The invention is further illustrated by the following preferred embodiments and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
The invention provides a composite microbial inoculant in a solidified form, preferably subjected to emulsification activation to obtain a soil conditioner, and provides technical equipment for providing biomass carbon materials for solidification for the microbial inoculant.
According to the invention, the composite soil conditioner comprises the following components in parts by weight:
0.1 to 2 parts of microbial inoculum,
10 parts of biobased pyrolytic carbon.
Preferably, the composite soil conditioner comprises the following components in parts by weight:
0.5 to 1 part of microbial inoculum,
10 parts of biobased pyrolytic carbon.
According to the invention, the microbial inoculum is a composite bacterial liquid formed by different strains, wherein the strains are selected from two or more of trichoderma, saccharomycetes, bacillus megaterium, photosynthetic bacteria, halomonas, bacillus subtilis and pseudomonas aeruginosa.
In a preferred embodiment, the bacterial species is selected from two or more of the group consisting of yeast, bacillus megaterium, halomonas, bacillus subtilis and pseudomonas aeruginosa.
According to the present invention, liquid seed strain is first cultured, preferably the seed strain is grown in an expanded culture to a cell concentration of 10 7 ～10 9 Liquid strain at a concentration of individual/mL. Then, the liquid strains are mixed to obtain the composite bacterial liquid.
According to the invention, the mass ratio of the liquid strains of the saccharomycetes, the bacillus megaterium, the halomonas, the bacillus subtilis and the pseudomonas aeruginosa is (2-5): (1-4): (2-4): (2-4): 1, preferably (2-4): (1-3): (2-3.5): (2-3.5): 1.
In the invention, the composite bacterial liquid with the types and the proportions is favorable for improving the repair efficiency and the repair quality of the polycyclic aromatic hydrocarbon organic pollution soil, and simultaneously can also improve the fertility of the soil and facilitate the absorption of mineral elements by plants.
According to a preferred embodiment of the invention, the bacterial agent or bacterial liquid obtained as above is solidified on a bio-based solid material, preferably pyrolytic carbon, also called semi-coke.
According to the invention, the bio-based solid material is in the form of granules, preferably mixed with other granules, preferably inorganic granules.
The mixing may be physical mixing of the semi-coke and the inorganic particulate material, each in the finished product, or in situ mixing during the preparation process.
According to the invention, said in situ mixing is carried out in a pyrolysis plant comprising a pyrolysis furnace 1, as shown in fig. 1, the plant carbon source entering the pyrolysis furnace 1 through a feed inlet 2, the resulting semicoke and the preliminary pyrolysis gas comprising carbon dioxide reacting with the calcium oxide in the additives, the final pyrolysis gas being discharged through a line 4 (optionally continuing as a source of heated gas), the calcium carbonate of the reaction product being discharged from the bottom with the semicoke, sent by a heat transfer means 5 to a cooling zone 6, contacted and conducted for heat exchange with the cooling gas entering through 8, the warmed flue gas being returned to the pyrolysis furnace 1 through a cyclone separator, merging with the purge gas entering through a gas supply line 3, the cooled product being collected through a discharge outlet 7. The feeding, pyrolysis, discharge, conveying and cooling of the semi-coke are finished, and the closed cycle of gas is realized.
In the present invention, the plant-based carbon source is a biomass material or material capable of providing carbon elements, preferably, the plant-based carbon source is selected from herbaceous plants or woody plants, the herbaceous plants may be agricultural biomass such as harvested or harvested crops such as straw, stalk or fruit shells, etc., aquatic plants such as reed or typha, vegetables or wild weeds, and the woody plants may be forestry biomass such as roots, branches, leaves of various trees, branches and leaves of shrubs, or other forestry waste or wood product waste.
According to the present invention, the vegetable carbon source is required to be appropriately treated, including drying and pulverizing.
In the present invention, the external moisture of the plant carbon source is removed by drying, such as by sun-drying or natural air-drying, and the plant carbon source is preferably air-dried so that the water content of the plant is 10% to 20%. And then chopped.
According to the invention, the plants are washed, preferably with deionized water, before they are dried, and then soaked in dilute hydrochloric acid.
In the present invention, the vegetable carbon source is pyrolyzed in a pyrolysis apparatus as shown in fig. 1, preferably at a medium and low temperature in a pyrolysis furnace 1. For this purpose, the vegetable carbon source supplied through the supply port may be pyrolyzed directly, preferably by purging with an inert gas (such as nitrogen or carbon dioxide gas) in advance, and then heated by an external heat source, and the temperature of the pyrolysis furnace is raised to 200 ℃ or higher, more preferably 300 to 600 ℃, for example 400 to 550 ℃.
In the invention, too low a temperature is unfavorable for volatilization and stripping of low-boiling-point organic matters, and higher temperatures are easy to cause excessive coking or complete carbonization. The process is maintained for tens of minutes to hours while maintaining a nitrogen flow to carry away gaseous products generated by pyrolysis while maintaining an anoxic environment.
The pyrolysis carried out by the invention mainly comprises three main stages of dehydration and drying, preheating and volatile component precipitation. Wherein, dehydration and drying refer to the removal of internal crystal water; then entering a short preheating stage, wherein the number of active structures of the raw material molecules is continuously increased; after preheating, volatile components are gradually separated out, light hydrocarbon compounds are continuously cracked and separated out to generate carbon monoxide, methane, hydrogen, carbon dioxide and the like, and the proportion of the residual fixed carbon is gradually increased. The crystal water, the generated volatile gas and most of tar steam (collectively called pyrolysis gas) can be discharged out of the pyrolysis furnace, the pyrolysis gas can be used as heating fuel, and the volatile gas liquid can be condensed and separated out, namely pyrolysis oil.
In the invention, the raw material feed inlet is sealed by the hydraulic device so as to prevent the leakage of pyrolysis gas and the infiltration of external air.
Preferably, the calcium oxide and/or calcium carbonate is added to the pyrolysis furnace either simultaneously with or after the addition of the vegetable carbon source, prior to separation of the carbocoal particles.
The reacted material is discharged and conveyed to a cooling area, and can be naturally cooled, preferably, the incandescent semicoke carbon is directly cooled by inert gas, so that semicoke carbon particles and hot gas are obtained. According to the invention, the cooling gas is preferably the same inert gas as the purge gas, and may be nitrogen, carbon dioxide, or a mixture thereof, with an amount of carbon dioxide contributing to the formation of calcium carbonate during pyrolysis.
According to the invention, the solid obtained by separation after cooling is pyrolytic carbon, i.e. semi-coke, and the bio-based carbon material is granular and comprises, in addition to semi-coke particles, calcium carbonate, part of which is derived from added calcium carbonate, and on the other hand from calcium carbonate formed from calcium oxide and carbon dioxide. The addition of calcification reduces the content of carbon dioxide in pyrolysis gas, and enables semicoke carbon particles and calcium carbonate to be mixed together, so that the density of particle materials is increased, meanwhile, the dispersion of semicoke carbon is promoted, agglomeration is avoided, and the uniformly distributed carrier material is compact and porous, so that the carrier material is very beneficial to the loading and solidification of bacterial liquid.
According to the invention, the carbocoal produced contains organic substances with higher boiling points and can be directly pressed into a certain shape, preferably with calcium carbonate.
According to a preferred embodiment, the semi-coke density is low, the mechanical strength is low, the semi-coke is easier to crush than the biomass raw material, and the crushing consumes less energy. For better shaping, it is therefore preferable to crush the semicoke carbon and then to press it into shapes such as microspheres, bars or rods, for example having a particle size or cross-sectional diameter of between 0.5mm and 10mm, preferably between 1mm and 5mm, for example between 2mm and 4mm. And the pyrolysis oil is more preferably pressed together with the obtained pyrolysis oil, so that the pyrolysis oil can play a role of an adhesive, carbon powder is easy to adhere, the situation that a formed product is loose is avoided, meanwhile, the pyrolysis oil is a pyrolysis product of a raw material, no additional material is needed to be utilized, the adhesion cost is reduced, on the other hand, heavy carbon organic matters in the pyrolysis oil are slowly decomposed or degraded in the soil improvement process, and carbon sources or nutrients are continuously provided, so that the effect of maintaining fertilizer and slowly releasing is generated, and the effective restoration of soil is promoted.
According to the preferred embodiment of the invention, the doped carbocoal obtained by the method is soaked in the bacterial liquid, so that the (doped) carbocoal has biological activity, and the soil optimizing effect is further improved.
According to the invention, load curing is mainly carried out by means of dipping. For this reason, the semicoke is immersed in the bacterial liquid for several hours, for example, 0.5 to 5 hours, preferably 2 to 3 hours, according to the actual situation. Preferably, the soaking is performed prior to application to the soil.
Then taking out the soaked semicoke carbon, and culturing for a period of time, preferably 5-30 h, preferably 12-18 h, at a preset temperature, preferably 30-35 ℃, so as to obtain the semicoke carbon with biological activity, wherein the calcium carbonate (sedimentation volume is about 2.4-2.8 mL/g) is lighter than the heavy calcium carbonate (sedimentation volume is about 1.1-1.9 mL/g) produced by a mechanical method, thus being light calcium carbonate and playing a good role in protecting the loaded strains.
According to the invention, an activator can be added at the same time or after soaking, and the activator consists of a solute and a solvent, wherein the solvent is water, and the solute comprises a carbon source, a nitrogen source, a phosphorus source and trace elements, and preferably comprises trimethylammonioethylene lactone and nitrilotriacetic acid.
In the invention, the components and the concentrations of the activator are as follows:
yeast powder (yeast extract) 0.2g/L, magnesium sulfate heptahydrate 0.2g/L, bean flour 0.88g/L, betaine 0.03g/L, microelements 0.02g/L, nitrilotriacetic acid 1.5g/L, corn starch 12g/L, sodium polyphosphate 3.5g/L. Preferably, the microelements comprise zinc sulfate heptahydrate, calcium sulfate dihydrate, boric acid, copper sulfate pentahydrate, sodium chloride, ferric chloride hexahydrate, EDTA, potassium chloride and potassium iodide, and the mass ratio of the corresponding components is preferably (20:20:5:8:5:6:1:0.03:7).
The inventor discovers that the semicoke carbon with biological activity and the activator are matched for use, so that the optimization effect of the organic polluted soil can be effectively improved, and meanwhile, the fertility of the soil can be improved.
According to the invention, the mass ratio of the composite soil conditioner to the soil to be optimized to be tested is (2-8): 100, preferably (3 to 5): 100.
examples
The invention is further described below by means of specific examples, which are however only exemplary and do not constitute any limitation on the scope of protection of the invention.
Example 1
The corn stalk is washed by water, soaked in 0.01M dilute hydrochloric acid for 2 hours, air-dried until the water content is 15-18%, and chopped. In a pyrolysis furnace, nitrogen is introduced for purging, then straw and a calcium mixture accounting for one fifth of the weight of the straw (the weight ratio of calcium oxide to calcium carbonate is 2:1) are added through a feeding port, the temperature is raised to 450-550 ℃, the heat preservation reaction is carried out for 2 hours, and meanwhile, the circulation of the nitrogen is kept.
Then cooling to room temperature to obtain semi-coke, crushing, and pressing with antipyretic oil obtained by condensing pyrolysis gas into granules with particle size of 2-4 mm.
Enlarging and culturing saccharomycete, bacillus megaterium, halomonas, bacillus subtilis and pseudomonas aeruginosa to obtain the bacterial concentration of 10 9 The liquid strains with the mass ratio of 2:1.8:3.2:3.2:1 are mixed, the activator is added, and the carbocoal particles are soaked in the bacterial liquid containing the activator for 3 hours and cultured in a constant temperature incubator at 30 ℃ for 15 hours, so that the composite soil conditioner is obtained.
Experimental example 1
The tested soil is about 5m 3 The soil is collected from a polluted site, and the sampling depth is 30-50 cm. The various aromatics used for the experiments were purchased from sigma corporation of the united states, all analytically pure. And selecting by manual screening, and taking a screen shot of 30mm as raw soil for a repair experiment. The specific physicochemical parameters of the soil are as follows, pH is 7.4-8, water content is 10%, porosity is 36.5%, vertical permeability coefficient is 1.78X10 － 3 cm/s, the soil texture is sandy silt, TOC is 1.18%, naphthalene content is 42mg/kg, benzopyrene content is 55mg/kg, and 5-6 polycyclic aromatic hydrocarbon content is 47 mg/kg.
The modifier is added according to the mass ratio of the composite soil modifier to the soil of 4:100, the pile is turned over regularly and water is properly supplemented in the repairing process, and meanwhile, indexes (including the content of polycyclic aromatic hydrocarbon, the biomass of degrading microorganisms and the structure of soil biological communities) are monitored, and the microbial inoculum, the nutrient solution and the like are regulated and added. After 3 months of treatment, the tested soil is tested, and the result shows that: the naphthalene removal rate in the tested soil reaches 85.3%, the benzopyrene removal rate reaches 82.0%, and the 5-6 polycyclic aromatic hydrocarbon removal rate reaches 86.4%.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention.
Claims (1)
1. The composite soil conditioner is characterized by being prepared by the following steps:
washing corn stalk with water, soaking in 0.01M dilute hydrochloric acid for 2 hr, air drying to water content of 15-18%, and cutting; in a pyrolysis furnace, nitrogen is introduced for purging, and then straw and a calcium mixture accounting for one fifth of the weight of the straw are added through a feeding port, wherein the weight ratio of calcium oxide to calcium carbonate is 2:1, heating to 450-550 ℃, and reacting for 2 hours while keeping the circulation of nitrogen;
then cooling to room temperature to obtain semi-coke, crushing, and pressing with antipyretic oil obtained by condensing pyrolysis gas into semi-coke particles with the particle size of 2-4 mm; enlarging and culturing saccharomycete, bacillus megaterium, halomonas, bacillus subtilis and pseudomonas aeruginosa to obtain the bacterial concentration of 10 9 The liquid strain of each mL is prepared from the following components in percentage by mass: mixing at a ratio of 1.8:3.2:1, adding an activating agent, soaking carbocoal particles in a bacterial liquid containing the activating agent for 3 hours, culturing in a constant temperature incubator at 30 ℃ for 15 hours to obtain a composite soil conditioner,
the activator comprises the following components in parts by weight:
yeast powder, namely yeast extract 0.2g/L, magnesium sulfate heptahydrate 0.2g/L, bean flour 0.88g/L, betaine 0.03g/L, microelements 0.02g/L, nitrilotriacetic acid 1.5g/L, corn starch 12g/L and sodium polyphosphate 3.5g/L, wherein the microelements comprise zinc sulfate heptahydrate, calcium sulfate dihydrate, boric acid, cupric sulfate pentahydrate, sodium chloride, ferric chloride hexahydrate, EDTA, potassium chloride and potassium iodide, and the mass ratio of the corresponding components is (20:20:5:8:5:6:1:0.03:7).
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