CN113698937A - Humic acid-earthworm-semicoke soil improvement technical method - Google Patents
Humic acid-earthworm-semicoke soil improvement technical method Download PDFInfo
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- CN113698937A CN113698937A CN202010444396.4A CN202010444396A CN113698937A CN 113698937 A CN113698937 A CN 113698937A CN 202010444396 A CN202010444396 A CN 202010444396A CN 113698937 A CN113698937 A CN 113698937A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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Abstract
The invention discloses a method for improving humic acid-earthworm-semicoke soil, which comprises the step of adding a composite soil conditioner into soil, wherein the composite soil conditioner comprises semicoke, humic acid and wormcast, the semicoke forming process is safe and environment-friendly, secondary pollution cannot be caused, the resource utilization rate of a plant source carbon source is improved, the semicoke is soaked by composite bacterial liquid, the degradation efficiency of organic pollutants in the soil is improved, the fertility of the soil is improved, the steps are simple, the operation is convenient, and the cost is lower.
Description
Technical Field
The invention relates to the technical field of soil improvement and restoration, in particular to a technical method for improving semi-coke soil by using humic acid, earthworm or wormcast.
Background
The organic pollution of soil refers to pollutants which are composed of natural organic matters existing in the forms of carbohydrate, protein, amino acid, fat and the like and some other biodegradable artificially synthesized organic matters. Polycyclic Aromatic Hydrocarbons (PAHs) are a class of toxic organic pollutants containing two or more benzene rings, which are widely distributed and stably exist in natural environments, and generally originate from atmospheric sedimentation, direct discharge of domestic sewage and industrial wastewater, surface runoff, leakage of petroleum and petroleum products, and the like. Organic pollution can destroy the original ratio of carbon, nitrogen and phosphorus in soil, soil is easy to harden, the pH value is changed, and the structure and the composition of the soil are destroyed, thereby bringing great negative effects to the ecological environment of polluted areas, crop production and human survival. Therefore, repairing and optimizing organically contaminated soil is an important task related to human survival.
The repair technologies adopted at present mainly comprise a gas phase extraction method, a thermal desorption method, a chemical leaching method, an oxidation-reduction method, a bioremediation method and the like, and the repair technologies for polluted sites such as polycyclic aromatic hydrocarbons and the like mainly comprise soil leaching, thermal desorption, chemical oxidation, bioremediation, phytoremediation technologies and the like. However, the method has the problems of poor removal effect, high cost, easy secondary pollution, long time consumption and the like. Therefore, it is necessary to provide a technical method for soil remediation and improvement with good organic pollutant removal effect.
Disclosure of Invention
In order to overcome the problems, the invention researches and discovers that: the soil conditioner prepared by adding the semicoke and the humic acid into the organic polluted soil and activating the semicoke by using the bacterial liquid, and the obtained conditioner can safely and efficiently improve the soil, thereby completing the invention.
Specifically, the invention aims to provide a method for improving humic acid-earthworm-semicoke soil, which comprises the step of adding a composite soil conditioner to soil, wherein the composite soil conditioner preferably comprises the following components in parts by weight:
semi-coke 10 parts
0.5-5 parts of humic acid, preferably 1-3 parts.
The semi-coke is in a granular shape and is preferably mixed with other granules, the granules are preferably inorganic granules, and the mixing can be that the semi-coke and the inorganic granules are respectively physically mixed in a finished product or in situ mixed in the preparation process.
According to the invention, the in-situ mixing is carried out in a pyrolysis furnace, in particular prepared according to the following method:
step 1, selecting a plant carbon source, preferably selected from herbaceous plants or woody plants, wherein the herbaceous plants can be agricultural biomass, such as harvested or harvested crops, aquatic plants such as reed or cattail, vegetables or wild weeds, and the woody plants can be forestry biomass.
And 2, pyrolyzing the plant carbon source to obtain the semi-coke.
In the invention, the plant carbon source is pyrolyzed in the pyrolysis equipment, preferably in a pyrolysis chamber of a pyrolysis furnace or device, preferably at a medium-low temperature, and can be directly pyrolyzed or blown with nitrogen for purging.
Preferably, calcium oxide and/or calcium carbonate is added to the pyrolysis furnace or chamber simultaneously with or after the addition of the plant carbon source, prior to separation of the semi-coke particles.
And 3, forming the granular material, directly pressing into a certain shape, and preferably pressing and forming together with calcium carbonate.
According to one embodiment of the present invention, the semi-coke or doped semi-coke can be soaked in a bacterial solution, so that the (doped) semi-coke has bioactivity.
In the invention, the bacterial liquid is a composite bacterial liquid and can be prepared according to the following method:
first, liquid seed culture is cultured. The strain is selected from one or more of azotobacter, saccharomycetes, bacillus megaterium, photosynthetic bacteria, bacillus subtilis and pseudomonas aeruginosa. In a preferred embodiment, the species is selected from one or more of yeast, bacillus megaterium, bacillus subtilis, and pseudomonas aeruginosa.
Then, the liquid strains are mixed to obtain the composite bacterial liquid.
In the invention, the mass ratio of liquid strains of saccharomycetes, bacillus megatherium, bacillus subtilis and pseudomonas aeruginosa is (2-5): (1-4): (2-4): 1.
In the invention, the soaking time of the (doped) semi-coke carbon in the bacterial liquid can be several hours, for example, 0.5 to 5 hours. Soaking is preferably performed prior to application to the soil.
And then, taking out the soaked semicoke, and culturing at a preset temperature, preferably 30-35 ℃ for a period of time, preferably 5-30 h to obtain the semicoke with biological activity.
In the invention, the humic acid is coal humic acid.
In the invention, the composite soil conditioner also comprises 0.5-1.5 parts of wormcast based on 10 parts of semi-coke by weight.
The invention also provides a soil conditioner obtained by the method, which comprises the following components in parts by weight:
semi-coke 10 parts
0.5-5 parts of humic acid, preferably 1-3 parts,
0.5-1.5 parts of wormcast.
The invention also provides the application of the conditioner for improving soil, wherein in the using process, the mass ratio of the composite soil conditioner to the soil is (1-10): 100, preferably (2-5): 100.
the invention has the advantages 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 avoided, the resource utilization rate of the plant source carbon source is improved, and organic pollutants in soil can be removed for a long time;
(2) according to the soil conditioner provided by the invention, the semicoke 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 meanwhile, the soil fertility is improved;
(3) according to the soil improvement method provided by the invention, the appropriate proportion of humic acid and wormcast is added into the conditioner, so that the degradation efficiency of organic pollutants in the soil is accelerated, and the fertility of the soil is improved;
(4) the soil improvement technical method provided by the invention has the advantages of simple steps, convenient operation, controllable conditions and lower cost.
Detailed Description
The present invention will be described in further detail below with reference to preferred embodiments and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used exclusively 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 method for improving humic acid/earthworm/semicoke soil, which comprises the step of adding a composite soil conditioner into soil.
According to a preferred embodiment of the invention, the composite soil conditioner comprises the following components in parts by weight:
semi-coke 10 parts
0.5-5 parts of humic acid.
Preferably, the composite soil conditioner comprises the following components in parts by weight:
semi-coke 10 parts
1-3 parts of humic acid.
According to the invention, the semi-coke is in the form of granules, preferably used in a mixture with other granules, preferably inorganic granules.
The mixing may be physical mixing of the semi-coke and the inorganic granules respectively in finished products, or in-situ mixing during the preparation process.
According to the invention, the in-situ mixing is carried out in a pyrolysis furnace, in particular prepared according to the following method:
step 1, selecting a plant carbon source.
The plant carbon source is biomass materials or materials capable of providing carbon elements, preferably, the plant carbon source is selected from herbaceous plants or woody plants, the herbaceous plants can be agricultural biomass, such as harvested or harvested crops, such as straws, straws or shells and the like, aquatic plants, such as reeds or cattails, vegetables or wild weeds, and the woody plants can be forestry biomass, such as roots, branches, leaves of various trees, branches and leaves of shrubs, or other forestry wastes or wood product wastes.
According to the present invention, the plant carbon source is subjected to appropriate treatments including drying and pulverization.
In the present invention, the external moisture of the plant carbon source is removed by drying, such as 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, and then soaked in dilute hydrochloric acid before they are dried.
And 2, pyrolyzing the plant carbon source to obtain the semi-coke.
In the present invention, the plant-based carbon source is pyrolyzed in a pyrolysis apparatus, preferably in a pyrolysis chamber of a pyrolysis furnace or device, preferably at a medium or low temperature. For this purpose, the plant carbon source is introduced into the pyrolysis furnace or chamber through the feed inlet, and may be directly pyrolyzed, or may be purged by introducing nitrogen gas and then heated by an external heat source to raise the temperature of the pyrolysis furnace or chamber to 100 ℃ or higher, preferably 200 ℃ or higher, more preferably 300 to 600 ℃, for example 400 to 550 ℃.
In the invention, the volatilization and stripping of low-boiling-point organic matters are not facilitated due to too low temperature, and excessive coking or complete carbonization is easily caused due to higher temperature. The process is maintained for several tens of minutes to several hours while maintaining the circulation of nitrogen to carry away the gaseous products generated by pyrolysis while maintaining an oxygen-deficient environment.
The pyrolysis is mainly carried out in three main stages of dehydration drying, preheating and volatile component separation. Wherein, dehydration drying refers to the removal of internal crystal water; then entering a short preheating stage, and continuously increasing the number of active structures of raw material molecules; volatile components are separated and separated out gradually after preheating, light hydrocarbon compounds are cracked and separated out continuously to generate carbon monoxide, methane, hydrogen, carbon dioxide and the like, and the proportion of the residual fixed carbon is increased gradually. The crystal water, the generated volatile gas and most of tar steam (collectively called pyrolysis gas) can be brought out of the pyrolysis furnace or the pyrolysis chamber by nitrogen, the pyrolysis gas can be used as heating fuel for pyrolysis, and volatile gas liquid can be condensed and separated out, namely pyrolysis oil.
In the invention, the raw material inlet and outlet of the pyrolysis chamber are closed and sealed by using a hydraulic device, and only an opening for nitrogen to enter and exit is reserved to prevent the outward leakage of pyrolysis gas and the infiltration of outside air.
Preferably, the calcium oxide and/or calcium carbonate is added into the pyrolysis furnace or the pyrolysis chamber at the same time or after the plant carbon source is added and before the semi-coke particles are separated, and the temperature is reduced after the pyrolysis is finished. In the invention, the temperature reduction can be carried out by natural cooling, or the red-hot semi-coke carbon can be directly cooled by normal-temperature nitrogen to obtain semi-coke carbon particles and hot nitrogen, and the hot nitrogen can be circularly used in the blowing process.
According to the invention, the solid pyrolytic carbon obtained by separation after temperature reduction is semi-coke, which is a granular material, and comprises calcium carbonate besides semi-coke granules, wherein a part of the solid pyrolytic carbon is derived from added calcium carbonate, and on the other hand, the solid pyrolytic carbon is derived from calcium carbonate formed by calcium oxide and carbon dioxide. The addition of the calcification reduces the content of carbon dioxide in the pyrolysis gas, and enables semi-coke particles and calcium carbonate to be mixed together, so that the density of the particle material is increased, and meanwhile, the dispersion of the semi-coke is promoted, and the agglomeration is avoided.
And 3, forming the granular material.
According to the invention, the produced semicoke contains organic substances with higher boiling points, can be directly pressed into a certain shape, and is preferably pressed and formed together with calcium carbonate.
According to the preferred embodiment, the semi-coke has low carbon density, low mechanical strength, and is easier to crush and consumes less energy for crushing than biomass raw materials. Thus, for better shaping, it is preferred that the semi-coke is crushed and then subjected to compression molding, such as micro-spheres, bars or rods, for example, having a particle size or cross-sectional diameter of 0.5mm to 10mm, preferably 1mm to 5mm, for example 2mm to 4 mm. The pyrolysis oil can play a role of an adhesive, so that carbon powder is easy to adhere, the loose situation of a formed product is avoided, meanwhile, the pyrolysis oil is a pyrolysis product of the raw material, no additional material is needed, the adhesion cost is reduced, and on the other hand, heavy carbon organic matters in the pyrolysis oil are slowly decomposed or degraded in the soil improvement process, and a carbon source or nutrient is continuously provided, so that the effect of fertilizer holding and slow release is generated, and the effective repair of soil is promoted.
According to one embodiment of the invention, the semi-coke or the doped semi-coke can be soaked in the bacterial liquid, so that the (doped) semi-coke has bioactivity, and the soil optimization effect is further improved.
In the invention, the bacterial liquid is a composite bacterial liquid and can be prepared according to the following method:
first, liquid seed culture is cultured.
According to the invention, the strain is selected from one or more of azotobacter, saccharomycetes, bacillus megaterium, photosynthetic bacteria, halomonas, bacillus subtilis and pseudomonas aeruginosa.
In a preferred embodiment, the species is selected from one or more of yeast, bacillus megaterium, bacillus subtilis, and pseudomonas aeruginosa.
More preferably, the strain is expanded to a cell concentration of 107～109one/mL of liquid seed culture.
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 megatherium, the bacillus subtilis and the pseudomonas aeruginosa is (2-5): (1-4): (2-4) 1, preferably (2-4): (1-3): (3-3.5) 1.
According to the invention, the composite bacterial liquid with the types and the proportions is adopted, so that the remediation efficiency and the remediation quality of the organic polluted soil can be effectively improved, the fertility of the soil can be improved, and the mineral elements can be absorbed by plants.
According to the present invention, the (doped) carbocoal is soaked in the bacterial liquid, and the soaking time can be several hours, for example, 0.5 to 5 hours, preferably 2 to 3 hours, according to actual needs. Preferably, the soaking is performed before application to the soil.
And then, taking out the soaked semicoke, and culturing at a preset temperature, preferably 30-35 ℃, for a period of time, preferably 5-30 h, preferably 12-18 h to obtain the semicoke with biological activity.
In the invention, the humic acid is coal humic acid, and can be common humic acid in the prior art, such as humic acid prepared from Xinjiang weathered coal produced by Shandong agricultural fertilizer science and technology Limited.
The inventor finds that the optimal effect of the organic contaminated soil can be effectively improved and the fertility of the soil can be improved by using the semi-coke carbon with biological activity and the humic acid in a matching way.
According to the invention, the composite soil conditioner also comprises wormcast, and preferably, the wormcast is 0.5-1.5 parts per 10 parts by weight of semi-coke.
In the invention, the earthworm cast or the earthworm soil is a biological fertilizer commonly used in the prior art, has the functions of improving soil, detoxifying, adsorbing and preventing plant diseases and insect pests, is tasteless, granular and good in water absorption and permeability, can be obtained by automatically feeding and breeding earthworms, for example, earthworms are bred in a specific soil area, and can also be commercially available as a biological fertilizer.
According to the invention, the mass ratio of the composite soil conditioner to the tested soil to be optimized is (1-10): 100, preferably (2-5): 100.
examples
The present invention is further described below by way of specific examples, which are merely exemplary and do not limit the scope of the present invention in any way.
Example 1
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. Introducing nitrogen into a pyrolysis furnace for purging, then adding straws and a calcium mixture (the weight ratio of calcium oxide to calcium carbonate is 2: 1) which accounts for one fifth of the weight of the straws through a feeding port, heating to 450-550 ℃, and carrying out heat preservation reaction for 2 hours while keeping the circulation of nitrogen.
And then cooling to room temperature to obtain semi-coke, crushing, and pressing with antipyretic oil obtained by condensing pyrolysis gas into granules with the particle size of 2-4 mm.
The yeast, the bacillus megaterium, the bacillus subtilis and the pseudomonas aeruginosa are subjected to amplification culture to form the thallus concentration of 109Mixing liquid strains per mL according to the liquid mass ratio of 2.5:1.8:3.2:1, soaking the semi-coke carbon particles in the bacterial liquid for 2 hours, and culturing in a constant-temperature incubator at 30 ℃ for 13 hours.
Mixing the activated semicoke particles with coal humic acid and wormcast according to the weight ratio of 10: 2:1, mixing to obtain the composite soil conditioner.
Experimental example 1
The tested soil is about 5m3The sample is collected from a certain polluted site, and the sampling depth is 30-50 cm. A plurality of aromatic hydrocarbons used in the experiment are purchased from sigma company in the United states and are all analytically pure. And selecting by manual screening, and taking the 30mm undersize as original soil for a restoration experiment. Specific physicochemical parameters of the soil, e.g.The pH value is 7.4-8, the water content is 10%, the porosity is 36.5%, and the vertical permeability coefficient is 1.78 multiplied by 10－ 3cm/s, the soil texture is sandy silt, the TOC is 1.18 percent, wherein the content of naphthalene is 38mg/kg, the content of benzopyrene is 50mg/kg, and the content of 5-6 polycyclic aromatic hydrocarbon is 43 mg/kg.
Adding the modifier according to the mass ratio of the composite soil modifier to the soil of 3:100, regularly turning and properly supplementing water in the repairing process, simultaneously monitoring indexes (including polycyclic aromatic hydrocarbon content, biomass of degraded microorganisms and soil biological community structure), and adjusting the added microbial inoculum, nutrient solution and the like. After 3 months of treatment, the soil to be tested is detected, and the results show that: the removal rate of naphthalene in the tested soil reaches 84.3%, the removal rate of benzopyrene reaches 86.0%, and the removal rate of 5-6 polycyclic aromatic hydrocarbon reaches 85.1%.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate 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, which fall within the scope of the present invention.
Claims (10)
1. A method for improving humic acid-earthworm-semicoke soil comprises the step of adding a composite soil conditioner into soil.
2. The method of claim 1, wherein the composite soil conditioner comprises the following components in parts by weight:
semi-coke 10 parts
0.5-5 parts of humic acid, preferably 1-3 parts.
3. The process according to claim 1 or 2, characterized in that the semi-coke is in the form of granules, preferably used in admixture with other granules, preferably inorganic granules,
the mixing may be physical mixing of the semi-coke and the inorganic granules respectively in finished products, or in-situ mixing during the preparation process.
4. A method according to claim 3, wherein the in-situ mixing is done in a pyrolysis furnace, preferably comprising the steps of:
step 1, selecting a plant carbon source selected from herbaceous plants or woody plants,
2, pyrolyzing the plant carbon source in pyrolysis equipment at a medium and low temperature, wherein the pyrolysis can be directly performed, or nitrogen can be firstly introduced for purging to obtain semi-coke,
and 3, pressing and forming the granular material.
5. The method according to claim 4, wherein, in step 2,
calcium oxide and/or calcium carbonate is added to the pyrolysis furnace or chamber simultaneously with or after the addition of the plant carbon source, prior to separation of the semi-coke carbon particles.
6. The method according to any one of claims 1 to 5, wherein the semi-coke is soaked with a bacterial liquid, and the bacterial liquid is a composite bacterial liquid.
7. The method according to claim 6, wherein the bacterial species is selected from one or more of azotobacter, yeast, Bacillus megaterium, photosynthetic bacteria, Bacillus subtilis, and Pseudomonas aeruginosa.
8. The method according to claim 7, wherein the mass ratio of the liquid strains of the yeast, the bacillus megaterium, the bacillus subtilis and the pseudomonas aeruginosa is (2-5): (1-4): (2-4): 1.
9. The method according to any one of claims 6 to 8, wherein the semi-coke is soaked in the bacterial liquid for 0.5 to 5 hours, preferably before application.
10. A soil amendment according to any one of claims 1 to 9, comprising the following components in parts by weight:
semi-coke 10 parts
0.5-5 parts of humic acid
0.5-1.5 parts of wormcast.
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