CN111792952A - Active coal gangue micro powder, active coal gangue mineral fertilizer and preparation method - Google Patents

Active coal gangue micro powder, active coal gangue mineral fertilizer and preparation method Download PDF

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CN111792952A
CN111792952A CN202010657574.1A CN202010657574A CN111792952A CN 111792952 A CN111792952 A CN 111792952A CN 202010657574 A CN202010657574 A CN 202010657574A CN 111792952 A CN111792952 A CN 111792952A
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coal gangue
fertilizer
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active
active coal
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苏文锦
苏文雯
苏斌
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Beijing Jinxiu New Technology Development Co ltd
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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00Other inorganic fertilisers
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05BPHOSPHATIC FERTILISERS
    • C05B7/00Fertilisers based essentially on alkali or ammonium orthophosphates
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05CNITROGENOUS FERTILISERS
    • C05C9/00Fertilisers containing urea or urea compounds
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05FORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F17/00Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
    • C05F17/20Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation using specific microorganisms or substances, e.g. enzymes, for activating or stimulating the treatment
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/80Soil conditioners
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/40Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse

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Abstract

The invention relates to active coal gangue micro powder, an active coal gangue mineral fertilizer, an active coal gangue nitrogen fixation mineral fertilizer and a full-element efficient coal gangue biological bacterial fertilizer, wherein the active coal gangue micro powder is prepared by mixing and grinding the following raw materials: 80 to 90 percent of coal gangue, 1.0 to 10.0 percent of sugar industry waste residue, 1.0 to 10.0 percent of organic acid, 0.5 to 3.0 percent of alkanolamine substance, 0.4 to 4.0 percent of polar additive, 0.5 to 3.0 percent of dispersant, 0.5 to 3.0 percent of surfactant and 1.0 to 10.0 percent of excitant. Based on the poor activity of the coal gangue, the activity of the coal gangue is changed by adopting the superfine treatment of the fly ash; surface modification is carried out by adding other raw material formulas, and the surface of the coal gangue is connected with active polar groups: amino, hydroxyl, carboxyl and the like, on one hand, provide physical conditions for the attachment and decomposition of the coal gangue by following biological bacteria. On the other hand, the grinding efficiency and the grinding quality are improved, the energy consumption is reduced, and the cost of the coal gangue fertilizer is reduced.

Description

Active coal gangue micro powder, active coal gangue mineral fertilizer and preparation method
Technical Field
The invention relates to the field of coal gangue and mineral fertilizers, in particular to a nitrogen fixation mineral fertilizer containing active coal gangue, a preparation method and a full-element efficient coal gangue biological bacterial fertilizer.
Background
The coal gangue is massive waste separated in the coal mining process or the coal scouring process, is one of the industrial solid wastes with the largest annual discharge amount and accumulated stockpiling amount in China at present, and accounts for about 15 percent of the coal yield. The total stock of coal gangue in the whole country reaches more than 30 hundred million tons day ago, 1000 gangue hills are formed, the land occupation is 1.2 ten thousand mu, and the discharge amount is still increased year by year at present. The stockpiling of a large amount of coal gangue not only pollutes the environment, but also occupies a large amount of land. At present, most of the technologies for preparing organic fertilizers or biological bacterial fertilizers by coal gangue are in laboratories and in the aspect of papers. The industrial production is not yet possible. The main reasons are that the technology is immature or imperfect. The main performance is as follows:
1. the preparation of the fertilizer from the coal gangue firstly needs to activate the coal gangue, the main method at present is high-temperature calcination, the temperature is 1050 ℃ at 550-. The calcination time is long, generally more than 2 hours, and the calcination fineness can only reach about 60 meshes; calcination is generally carried out using light limestone (CaCO)3) Anhydrous sodium carbonate (Na)2CO3) And 3 kinds of assistants of caustic soda (NaOH) particles, wherein the principle is that after the 3 kinds of assistants are added into a kaolinite sample and uniformly mixed, in the calcining process, the firm Si-O and Al-O bond structures in the natural coal gangue are destroyed, so that silicon in the natural coal gangue is activated. However, the pH of the produced finished product is too high, and the finished product is not suitable for many soils and plant growth.
2. The fertilizer has low fertilizer efficiency (low nitrogen content), and due to the difference between the activation temperature and coal gangue in various regions, insufficient activation temperature causes that a plurality of mineral elements are not fully activated without dissociation and the expected effect is not achieved, or excessive fire sintering generates new inactive substances which can not be absorbed by plants.
3. The microbial method is greatly influenced by the methods 1 and 2. In addition, the currently selected strains are single, most of the strains concentrate on phosphorus and potassium dissolving strains, and the strains have high requirements on environmental conditions and can only stay in a laboratory and cannot be industrially produced; the growth condition of the bacteria is high, and the bacteria are easily polluted by other mixed bacteria; the bacteria are heterotrophic bacteria, organic nutrients such as glucose, cane sugar and the like are needed for growth and propagation, and the excellent characteristics of the strains are difficult to maintain for a long time and easy to degrade due to overhigh cost in industrial production, and the strains must be replaced irregularly to maintain high productivity.
4. The inoculation technology converts indissolvable phosphorus and potassium existing in mineral form in the coal gangue into available phosphorus and potassium available for plants, but other nutrient elements cannot be utilized to cause incomplete fertilizer efficiency, the content of phosphorus and potassium in the coal gangue directly influences the available phosphorus and potassium of the fertilizer, and the organic fertilizer produced by the method has little meaning.
5. Most importantly, the coal gangue contains a certain amount of heavy metals, the amount of the heavy metals is controlled by controlling the usage amount of the coal gangue, the consumption of the coal gangue can be greatly reduced, the environment pollution caused by the coal gangue is reduced by consuming the coal gangue, and the fertilizer has no market value in production.
Disclosure of Invention
The invention aims to solve the technical problem of providing active coal gangue micro powder, an active coal gangue mineral fertilizer, a preparation method thereof and a full-element high-efficiency coal gangue biological bacterial fertilizer.
The technical scheme for solving the technical problems is as follows: an active coal gangue micropowder is prepared by mixing and grinding the following raw materials: 80 to 90 percent of coal gangue, 1.0 to 10.0 percent of sugar industry waste residue, 1.0 to 10.0 percent of organic acid, 0.5 to 3.0 percent of alkanolamine substance, 0.4 to 4.0 percent of polar additive, 0.5 to 3.0 percent of dispersant, 0.5 to 3.0 percent of surfactant and 1.0 to 10.0 percent of excitant.
The invention has the beneficial effects that:
1. the invention adds the sugar-making industrial waste residue into the coal gangue, and when grinding, the coal gangue has stronger polarity and good adsorption effect because of containing substances with OH, C00H groups and other groups, and is adsorbed on crystal nuclei of the coal gangue, and the force on the surface of the coal gangue is unsaturated and has free surface tension. The adsorption of the carbohydrate molecules on the surface of the solid particles saturates this free surface tension, reducing the surface energy, as a result of which the structural properties of the particle surface are changed, reducing the strength and hardness of the particle, i.e. the molecular fracture tension, while preventing the closure of new cracks and accelerating the propagation of cracks in the material.
Meanwhile, the added industrial sugar residues are uniformly adsorbed on each coal gangue particle through high-speed and full dispersion, and become nutrient carbon sources and energy sources of the fungi. When the biological bacteria adsorb and convert the saccharides, the coal gangue particles are fully dissociated and decomposed.
2. Organic acid is added in the ground coal gangue material, and because the organic acid introduces active functional groups such as-COOH, -0H, acid radical ions and the like, the organic acid is very easy to be combined with Ca2+ in cement, so that the valence bond force is shielded, the cracks of particles are enlarged by penetrating the interior of the solid, the binding force among the particles is reduced, and the grinding effect is improved; when the coal gangue filler is used in coal gangue, the plastic deformation of materials can be accelerated, the strength of the materials can be reduced, the phenomena of material agglomeration and wall adhesion can be prevented, and the application performance of products can be improved.
The application of the organic acid increases the concentration of H + in the coal gangue, and acidifies the coal gangue, thereby reducing the pH value of the coal gangue. The pH value of the coal gangue treated by the low-concentration malic acid and the citric acid is higher than the initial pH value of the coal gangue in the initial stage, and the pH value is basically gradually reduced to be lower than the initial pH value along with the increase of the concentration of the organic acid and the prolonging of the culture time, and the acidification effect is generally expressed that the malic acid is larger than the citric acid.
The organic acid is used as a carbon source of the microorganism bacteria, nutrient substances are provided for the survival and the activity of the microorganism in the coal gangue with relatively deficient nutrients, the activity of the microorganism is enhanced, the nitrogen component which cannot be utilized by the microorganism in the coal gangue can be continuously converted into an effective form through the metabolism of the microorganism, and meanwhile, the effective nitrogen component in the body can be released into the coal gangue through the propagation and death of the microorganism, so the content of alkaline hydrolysis nitrogen in the coal gangue is obviously increased within a certain time.
The organic acid may have a certain particle crushing effect on the coal gangue, so that the weathering and soil-forming process of the coal gangue is accelerated, the release of nitrogen is accelerated, the release of alkaline hydrolysis nitrogen of the coal gangue can be accelerated under a humid condition, and the longer the humid condition is kept, the more obvious the promotion effect is. Under the condition that the coal gangue is wet, the release of alkaline hydrolysis nitrogen of the coal gangue can be further promoted by adding acid with low molecular weight in a combined manner.
The long-term moisture infiltration has an inhibition effect on the release of the coal gangue quick-acting potassium, the release of the coal gangue quick-acting potassium can be further inhibited in a short time due to the existence of the organic acid, the inhibition effect of moisture on the release of the coal gangue quick-acting potassium can be relieved due to the long-term existence, and the organic acid can dissolve and convert mineral potassium in soil through an acidification effect, a coordination exchange effect and a reduction effect, so that the release of potassium is promoted, and the biological effectiveness is improved.
The organic acid has an activating effect on the quick-acting phosphorus component in the coal gangue, and the addition of the organic acid increases the quick-acting phosphorus content of the coal gangue to a certain extent. The mechanism of organic acid activating phosphorus mainly comprises: acid dissolution; the complex reaction is carried out between the iron oxide and the hydrate in the soil, the electric charge on the surface of the adsorbents is changed, and the adsorption and fixation of the soil to phosphate radicals are reduced; compete for complexing sites with phosphate radicals, so that the adsorption of the soil to the phosphate radicals is reduced; removing the P adsorption sites of the soil; the complex reaction between the anions and metal ions such as Fe, Al and Ca causes the dissolution of the P-containing compound, thereby activating the phosphorus in the soil.
3. Adding an alkanol amine substance, wherein the molecule of the alkanol amine substance contains amino and hydroxyl, and has the comprehensive performance of amine; the coal gangue self-adhesive agent can be automatically attached to the surface of the coal gangue through a complex reaction with minerals difficult to hydrate. The coal gangue solid surface layer molecules have residual force as the liquid surface molecules, and the solid does not have fluidity, so the surface energy cannot be reduced like a way of reducing the surface area of liquid as much as possible. The adsorption is carried out automatically, and the adsorption conditions of different solid materials and different adsorbents are different.
In the process of crushing the coal gangue solid material, if the grinding-aid substances with grinding-aid property are not added, when the coal gangue solid material is ground to be below dozens of microns, the particles are very small, the specific surface area is very large, and the system has very large surface energy and is in thermal powerA chemically unstable state, in which the surface energy is reduced only by the surface becoming smaller automatically, i.e. the particle agglomeration becoming larger. When the ionic bonds of the particles are broken during the pulverization process, Ca is generated when CaO is broken2+And O2-The positively and negatively charged particles will also agglomerate, enlarging the particles. If the substance is added in the crushing process, molecules of the substance can be automatically adsorbed to the surfaces of the particles, the surface energy is reduced, the charges on the particles are shielded, the agglomeration of small particles is prevented, the fluidity of the material is increased, and the grinding efficiency is enhanced.
4. Adding polar additive, wherein the polar additive is mainly hydroxyl-containing nonionic surfactant. The surfactant containing polar group micromolecules is added in the coal gangue grinding process, polar molecules can be automatically adsorbed to the surfaces of the particles, the surface energy is reduced, charges on the particles are shielded, the agglomeration of the small particles is prevented, the fluidity of materials is increased, and the grinding efficiency is enhanced. The effect of the ethylene glycol on the coal gangue is obvious, and the fineness of the coal gangue can be greatly reduced.
5. The addition of the exciting agent has the effects of acting on the surfaces of the coal gangue particles through physical or chemical adsorption, effectively reducing the surface free energy of material particles, avoiding the healing of cracks to promote the expansion of the cracks, reducing the friction force and the adhesion force among the particles, enabling the sliding among the particles to be easy, particularly playing a good role in fine grinding, and effectively prolonging the grinding limit. The content of particles less than or equal to 15um in the coal gangue can be increased by 20 percent, along with the more reasonable gradation of coal gangue particles and the increase of trace active ingredients, the gradation of the coal gangue particles is effectively improved, the spheroidization of the coal gangue particles is promoted, the roundness coefficient of the coal gangue particles is improved, the coal gangue particles and aluminum, silicon, calcium and the like in the coal gangue are subjected to chemical reaction to generate intermediate substances with active functions, and meanwhile, the oxide lattice defect in the coal gangue is caused, and the activity is increased.
6. The dispersant is added, so that the surface energy of the particles is reduced or dislocation migration of a near-surface layer lattice is caused by adsorption on the surface of the coal gangue, and the defects of points or lines are generated, thereby reducing the strength and hardness of the particles; meanwhile, the closing of the new cracks is prevented, and the expansion of the cracks is promoted. The dispersant enables zeta potential on the surface of the coal gangue powder to be larger by adjusting rheological property of the mineral powder, surface electrical property of mineral particles and the like, increases repulsive force among powder, reduces viscosity of the coal gangue powder, promotes dispersion of particles, improves flowability, and prevents mineral particles from being adhered to a grinding medium and a lining plate of a mill and agglomeration among the particles.
7. The surfactant is added, so that the coal gangue particle dispersing agent has obvious dispersibility on coal gangue particles, and the flowing speed of materials is improved in the coal gangue powder grinding process. Effectively prevent the agglomeration of the ground gangue powder.
Based on the poor activity of the coal gangue, the activity of the coal gangue is changed by adopting the superfine treatment of the fly ash; surface modification is carried out by adding other raw material formulas, and the surface of the coal gangue is connected with active polar groups: amino, hydroxyl, carboxyl and the like, on one hand, provide physical conditions for the attachment and decomposition of the coal gangue by following biological bacteria. On the other hand, the grinding efficiency and the grinding quality are improved, the energy consumption is reduced, the cost of the coal gangue fertilizer is reduced, and the utilization of the coal gangue is increased.
On the basis of the technical scheme, the invention can be further improved as follows.
The active coal gangue micropowder is prepared by crushing coal gangue into blocks with the size less than or equal to 50mm by a crusher; the particle size of the micro powder reaches 2000-3000 meshes.
The active coal gangue micropowder further comprises one or more than two of organic acid malic acid, oxalic acid, citric acid, humic acid, acrylic acid, polyacrylic acid, polycarboxylic acid, maleic anhydride, acetic acid or benzoic acid.
Based on the introduction of active functional groups such as-COOH, -0H, acid radical ions and the like into the organic acid, the organic acid is very easy to react with Ca in cement2+Bonding, shielding the valence bond force, penetrating the inside of the solid to increase the particle cracks, reducing the bonding force among crystal grains and improving the grinding effect; when the coal gangue filler is used in coal gangue, the plastic deformation of materials can be accelerated, the strength of the materials can be reduced, the phenomena of material agglomeration and wall adhesion can be prevented, and the application performance of products can be improved. The pH value of the coal gangue treated by oxalic acid is higher than the initial pH value,the pH value difference and change of the coal gangue are much higher than those of the citric acid and malic acid treatment, and the three reasons are mainly as follows:
firstly, the pH value of the coal gangue after being cultured is reduced due to the separation of H + by organic acid, the chemical structures of the organic acid with different molecular weights are not completely the same, the quantity of carboxyl and hydroxyl is different, and the difficulty of separating H + is also different;
secondly, the main component of the coal gangue is carbonaceous mudstone, and the weathered coal gangue after treatment and refinement has certain buffering performance which is mainly reflected in the early stage (or early stage) of treatment, so that the pH value is higher in the initial stage; thirdly, the coal gangue is not soil after all, and also does not have the property of the soil completely, and the pH value of oxalic acid treatment is far higher than that of malic acid and citric acid treatment due to the structural composition and the element composition of the coal gangue. Oxalic acid is used as dibasic acid, and the coordination groups are relatively reduced, so that the acidification effect is not as strong as malic acid and citric acid; or may be related to the activity of the microorganism. And the dibasic acid (especially inorganic acid) has certain effect of inhibiting the release of alkaline hydrolysis nitrogen of the coal gangue. Moreover, the coal gangue treated by the low molecular weight acid malic acid and the citric acid is in subacidity, which is beneficial to the stabilization of the alkaline nitrogen-hydrolyzing nutrient released by the coal gangue in a medium, and the micro-alkalinity of the coal gangue treated by the oxalic acid is not beneficial to the stable existence of the alkaline nitrogen-hydrolyzing.
Humic acid and polycarboxylic acid or a mixture thereof are preferred. Under the water immersion, the pH (neutral and alkaline level) and the conductivity of the coal gangue are increased due to the release of certain nutrients and basic ions. Moisture infiltration can promote the release of nitrogen nutrients, but has an inhibiting effect on the release of phosphorus and potassium nutrients; the preferable addition of humic acid can further promote the release of nutrients and basic ions in the coal gangue, has positive effects on the release of nitrogen, phosphorus and potassium nutrients, further increases the pH of the coal gangue, and reduces the conductivity of the buffer solution by forming a complex compound of the humic acid and the basic ions. The effect is more obvious when the concentration of the added humic acid is higher; after the humic acid is added, the coal gangue mainly shows that soluble nutrients enter a solution in a short period, exchange action is gradually generated along with the time extension to release exchanged nutrients, a dynamic complexing balance system of the humic acid and basic ions thereof is formed, and finally a relatively stable state is achieved; the coal gangue has high contents of organic carbon, total nitrogen, total potassium and available phosphorus, has high potential of supplying nutrients, and the addition of humic acid can improve the plant availability of the coal gangue nutrients.
When the humic acid bacteria are applied to the bacterial fermentation fertilizer, the bacterial takes the humic acid as a carbon source, and the propagation speed and the quantity of beneficial bacteria are increased under the growth environment of the humic acid, so that the beneficial bacteria in the biological bacterial fertilizer can play a greater role. The nutrient supply of crops is changed by using the life activities and metabolic products of microorganisms, and nutrient elements and growth substances are provided for the crops; the humic acid amine is an ideal ammonia stabilizer, and quinone group in the humic acid has the function of a urease inhibitor, can inhibit the activities of soil urease and nitrobacteria, and effectively controls the speed of decomposition and release of nitrogen; the humic acid has the functions of improving soil, enhancing fertilizer efficiency, stimulating growth, enhancing stress resistance and improving quality, has the properties of a drought resistant agent, a growth regulator, a pesticide slow-release synergist and a chemical element complexing agent, and can be used as a fertilizer synergist, a soil regulator, a rhizosphere growth stimulating agent and the like.
Preferably a polycarboxylic acid, which is a surface active acid. The molecular structure is a comb-shaped structure, the main chain contains polar groups, and the side chain contains polyoxyethylene chain segments. Polar groups in the molecular structure of the polycarboxylic acid, such as carboxylic acid groups, sulfonic acid groups, amide groups and the like, can be adsorbed on the surface of the material, and active points of the material generated in the grinding process are shielded through charge repulsion to prevent the composition of a fracture surface; the powder grinding aid is firmly adsorbed on the surfaces of material particles, so that the material particles are not bonded with each other, and can quickly permeate into cracks of the particles, so that the healing effect generated by molecular force is weakened, the expansion of the cracks in the particles when the outside does work is promoted, and the grinding efficiency is improved.
According to the griffy law, the minimum stress required for brittle fracture is proportional to the specific surface energy of the material. Obviously, lowering the surface energy of the particles reduces the stress required to fracture them. From the process of particle fracture, the adsorption of the polycarboxylic acid molecules on the new surface can reduce the stress of crack propagation and promote the crack propagation. The polyoxyethylene chain segment of the side chain has certain steric hindrance effect, can form stereo crossing, prevents the particles from approaching each other, forms space obstruction, and achieves the purposes of improving the grinding effect and reducing the energy consumption.
In the active coal gangue micropowder, the alkanolamine substance is one or more of monoethanolamine, dipropanolamine, tripropanolamine, dibutanolamine, tributanolamine, triethanolamine, diethanolamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, 2-dihydroxy dipropylamine, triethanolamine disulfonate, polyacrylamide or potassium polyacrylate.
The substance has a pair of unshared electrons due to the N atom in the molecule, and can easily form a covalent bond with metal ions to be complexed; form relatively stable complexes with metal ions, and the complexes form a plurality of soluble areas in solution. The specific area is increased, the fineness is reduced, the grinding aid effect of flow rate is accelerated in the coal gangue grinding process, amines are growth factors of animals and microorganisms, and the amine substances selected by the invention are used as the growth factors of the microorganisms in the whole preparation process.
The active coal gangue micropowder is prepared from one or more of molasses, sugar residue, calcium sulfate, bagasse, beet waste liquid, syrup, paper pulp waste liquid, corn syrup, lactose, glucose and glucoside.
In the active coal gangue micropowder, the polar additive is any one or more than two of xylitol, diethylene glycol, propylene glycol, glycerol, ethylene glycol, diethylene glycol, sorbitol, sodium gluconate, sodium glycolate or sodium citrate.
The active coal gangue micropowder is prepared from one or more of ammonium nitrate, citric acid residues, urea, calcium phosphate, calcium nitrate, potassium carbonate, monopotassium phosphate, calcium phosphate residues, potassium sulfate, potassium sulfite, calcium sulfite, zinc sulfate, borax, molybdenum sulfate, copper sulfate, ferric sulfate and EDTA.
The active coal gangue is used for nitrogen fixation fertilizer, and most of the excitants are mineral elements required by plant growth. Meanwhile, the microorganism needs elements such as phosphorus, sulfur, magnesium, calcium, potassium, sodium, iron, zinc, cobalt, molybdenum, copper, manganese, nickel, tungsten and the like besides a carbon source, an energy source and a nitrogen source. Wherein the element is required to be in a concentration of 10-4~10-3Weighing major elements within the mol/L range; the required concentration is 10-8~10-6Trace elements are called in mol/L range. The former, such as phosphorus, sulfur, magnesium, calcium, potassium, sodium, iron, and the like; such as zinc, cobalt, molybdenum, copper, manganese, nickel, tungsten, and the like. The elements are mostly provided in the form of inorganic salts, so they are called inorganic salts or mineral elements. Although inorganic salts are required in much smaller amounts than C, N, the growth and metabolism of the microorganism is also important. Their physiological functions include: one of the important elements in the cytochemical composition of microorganisms, such as P and S, which are important constituent elements of nucleic acids and sulfur-containing amino acids (cysteine and methionine), respectively: ② related to the composition and activity of enzyme, for example, Fe is an essential component of cytochrome oxidase, Mg, Cu and Zn are activators of many enzymes: regulating and maintaining the growth conditions of the microbe, such as osmotic pressure, hydrogen ion concentration, oxidation-reduction potential and the like, for example, Na and K have the function of regulating the osmotic pressure of cells, and a buffering agent consisting of phosphate can keep the stability of the pH value in the growth process of the microbe: glutathione can reduce the oxidation-reduction potential; fourthly, the product is taken as an energy substance of certain chemoautotrophic bacteria; fifthly, the hydrogen acceptor is used as the end of the respiratory chain.
The active coal gangue micropowder further comprises one or more than two of trisodium phosphate, sodium hexametaphosphate, sodium tripolyphosphate, sodium gluconate, sodium pyrophosphate, sodium citrate, sodium humate, sodium fulvate and sodium dihydrogen phosphate serving as a dispersing agent.
The active coal gangue is used for nitrogen fixation fertilizer, and the phosphorus salt provides active phosphorus for fertilizer and plant growth under the phosphate dissolving action of microorganism.
In the active coal gangue micropowder, the surfactant is one or more than two of sodium dodecyl benzene sulfonate, lignin, sodium lignosulphonate, calcium lignosulphonate and paper mill waste liquid.
The lignin and lignin sulfonate derivatives thereof in the surfactant are natural polymer organic compounds with a net structure, have a large number of active groups and strong adsorption capacity, and can be chemically reacted with nitrogen, phosphorus, potassium and the like necessary for crop growth and physically adsorbed to synthesize an organic-inorganic compound fertilizer. The nutrient release in the fertilizer is carried out along with the decay of lignin in the nature, and the lignin is slowly degraded in the soil, so the fertilizer has stronger slow release property.
The invention also provides an active coal gangue mineral fertilizer which comprises the following raw materials in parts by weight: 980 parts of active coal gangue micropowder 960, 1-10 parts of organic acid, 1-10 parts of industrial waste residue, 10.5-5 parts of compound microbial inoculum B, 20.4-4 parts of compound microbial inoculum B, 32-8 parts of compound microbial inoculum B, 3-10 parts of microbial growth factor, 0.3 part of urea and 0.2 part of monopotassium phosphate.
According to the invention, the composite functional microbial bacteria are used for carrying out phosphorus and potassium dissolving and mineral element and trace element releasing treatment on the active coal gangue powder, so that the usage amount of the coal gangue is effectively utilized, the condition beneficial to microbial growth and fermentation is achieved, and the fertilizer capable of effectively utilizing nutrients is prepared.
The active coal gangue mineral fertilizer is characterized in that the composite microbial agent B1 is a mixed bacterium consisting of two or more of bacillus megaterium, bacillus amyloliquefaciens, bacillus licheniformis, bacillus subtilis, bacillus thuringiensis, bacillus badius, silicate bacteria, bacillus mucilaginosus, bacillus atrophaeus, bacillus circulans and bacillus laterosporus with phosphate and potassium dissolving functions;
the composite microbial inoculum B2 is a mixed bacterium of two or more than two of saccharomyces cerevisiae, pseudomonas, lactobacillus casei, aspergillus, trichoderma, achromobacter, rhizopus, flavobacterium, proteus, serratia, arthrobacter or streptomyces;
the compound microbial inoculum B3 is azotobacter chroococcum, azospirillum lipolyticum, bradyrhizobium nodorum, nitrorhizobium rhizobium stemorum, mesorhizobium baiviense, azospirillum brasiliensis, azotobacter bailii, azotobacter vinelandii, azotobacter paspalum, azotobacter indicum; two or more of Acidithiobacillus caldus, leptospirillum ferrooxidans, thermoferritin phaga, Acidithiobacillus ferrooxidans, Candida, Acidithiobacillus thiooxidans or Acidithiobacillus thiooxidans.
Two or more than two composite microbial agents B1 are compounded, and the volume ratio of the microbial agents can be 1: 1, culturing the compound microbial inoculum according to a known method (after each microbial inoculum is separated and purified for multiple times, the microbial inoculum is activated once on a culture medium inclined plane and then transferred into a liquid culture medium for shake culture for 3-5 days at the rotating speed of 200r/min and the temperature of 3O-50 ℃), preparing mixed strains into a bacterial suspension on the known culture medium inclined plane, and finally, the concentration of a single bacterium reaches 1 multiplied by 107~2×1014cfu/mL, the concentration of the compound bacteria reaches 1 multiplied by 107~6×1014cfu/mL。
The invention selects the bacteria mainly comprising bacillus with phosphate and potassium dissolving functions based on the composite microbial inoculum B1, the coal gangue contains rich organic matters and nitrogen, phosphorus and potassium, but the nitrogen, phosphorus and potassium in the coal gangue mostly exist in the form of indissolvable minerals, and the effective nitrogen, phosphorus and potassium content which can be directly absorbed and utilized by plants is very low. The method utilizes the compound floras with the potassium-dissolving function to process the chemical coal gangue together, so that the ineffective nitrogen, phosphorus and potassium are converted into the effective nitrogen, phosphorus and potassium to produce the coal gangue fertilizer. Further dissociation and decomposition of the active coal gangue are carried out while phosphate and potassium are dissolved.
The mass ratio of the inorganic phosphorus decomposing microbial inoculum to the organic phosphorus decomposing inorganic microbial inoculum in the compound microbial inoculum B2 can be selected to be 1.5: 1-3: 1; the culture method is carried out according to a known method: after each bacterial agent is separated and purified for many times, the bacterial agents are activated once on a culture medium inclined plane, and the compound bacterial agent B2 is prepared into bacterial suspension on a known culture medium inclined plane.
The bacillus has excellent phosphate and potassium dissolving function, strong organic phosphorus decomposing capacity and antagonistic effect on various pathogenic bacteria. The phosphate-solubilizing bacteria have the functions of inhibiting or reducing the propagation chance of pathogenic microorganisms and antagonizing the pathogenic microorganisms. The microbial phosphorus-dissolving capacity is suitable for soil culture or sand culture, so that the selection of the activated coal gangue powder directly mixed with the activated coal gangue powder is very favorable for the microbes to dissolve insoluble or insoluble phosphorus in the coal gangue. The period required for decomposing inorganic phosphorus is relatively long.
The composite bacterial liquid B2 is mainly used for decomposing inorganic phosphorus and organic phosphorus. 1-5% of phosphorus content in coal gangue, most of phosphorus and Si in coal gangue4+、Ca2+、Fe2+、Fe3+、Al3+The phosphate solubilizing mechanism of the microorganism is under an acidic environment or because the microorganism secretes organic acid, the acid can reduce the pH value and can be combined with ions such as iron, aluminum, calcium, silicon and the like, so that the insoluble phosphate is dissolved, and other minerals and metals are dissociated and decomposed. The invention selects organic acid in the coal gangue surface active treatment and the active coal gangue mineral fertilizer formula, and takes full consideration of the assistance of inorganic phosphorus decomposition, the action size of the organic acid depends on the type and the quantity of the acid, the buffering property of the formula and the quantity of ions capable of chelating phosphate radical ions, especially Ca in the active coal gangue2+More or less.
Based on phosphate solubilizing bacteria, NH is only contained in the medium4+When present, has the ability to dissolve inorganic phosphate. The invention selects amine compounds and ammonium salts in the coal gangue surface active treatment and the above 2.1 formula, and fully considers the assistance of inorganic phosphorus decomposition.
Based on the most direct action of the phosphate-solubilizing microorganisms, the phosphate-solubilizing microorganisms are used for dissolving insoluble or insoluble phosphorus in the coal gangue, and have the advantages that (1) the absorption of crops to other nutrient elements is promoted, and the phosphate-solubilizing microorganisms can adsorb surrounding trace elements such as zinc, copper and calcium, so that the plant nutrition is improved; but also can secrete growth regulating substances to promote the growth of root systems; (2) the fertilizer efficiency is high. The phosphate-solubilizing microbial fertilizer dissolves the insoluble phosphorus in the coal gangue and provides plants with high-quality phosphorus compounds which can be directly absorbed and utilized, and a considerable part of chemical fertilizer is lost due to the fixation effect in the application process; (3) and the environmental pollution is reduced. Because the high-quality phosphate-solubilizing microorganisms are directly separated from the coal gangue and used as the fertilizer, no pollutant is discharged to the environment in the production process, and the phosphate-solubilizing microorganisms are environment-friendly fertilizers in the true sense; (4) the phosphate-solubilizing microbial fertilizer has the advantages of simple production process, low investment, quick response, good benefit and strong market competitiveness.
The active coal gangue mineral fertilizer further comprises a microbial growth factor including biological enzyme and nutrient substances, wherein the mass ratio of the biological enzyme to the nutrient substances is 0.5: 1-2: 1; the biological enzyme can be selected from two enzymes in a mass ratio of 1: 1, or a mass ratio of 1: 1, the activity of the biological enzyme is maintained between 0.5 and 10 million u/g. The nutrient substances can comprise any more than two of vitamins, amino acids, basic groups, porphyrin and derivatives thereof, sterol, amines, yeast extract, peptone, wort or corn steep liquor; the biological enzyme can be any two of catalase, laccase, urease, neutral protease, polyphenol oxidase, phytase, cellulase, xylanase, protease and pectinase; the biological enzyme can also be selected from animal and plant tissue or cell immersion liquid, microorganism growth environment extract liquid, etc.
The main functions of the microbial growth factors of the present invention are to provide the components of important chemical substances (proteins, nucleic acids and lipids), cofactors (coenzymes and prosthetic groups) of microbial cells and to participate in metabolism. Most fungi, actinomycetes and some bacteria do not need to take any growth factors from the environment during their growth. Some microorganisms need to obtain one or more growth factors from the environment to maintain normal growth, for example, the lactic acid bacteria need multiple vitamins, amino acids and bases for supplement; the enzyme is a protein and has the functions of activation, catalysis, regulation, transfer and the like. The enzyme is added into the coal gangue fertilizer, so that various mineral elements in the active coal gangue can be activated, and the utilization rate of the fertilizer is greatly improved.
The invention also provides a preparation method of the active coal gangue mineral fertilizer,
step (1), according to the raw materials of the active coal gangue mineral fertilizer;
step (2), carrying out immobilization coating treatment on the compound microbial inoculum B1 to obtain a coated microorganism compound microbial inoculum B1;
step (3), adding active coal gangue micro powder, organic acid, industrial waste residues, microbial growth factors, urea and potassium dihydrogen phosphate into a dispersion machine according to the mass ratio, uniformly mixing, adjusting the water content to be 50-65%, adjusting the pH value to be 7-8, and adding a coated microbial composite bacterial agent B1 (the bacterial inoculation amount is 1.0 multiplied by 10)7-6.0×1014/g), adding the mixture into the mixture, stirring uniformly, and adding the compound microbial inoculum B2 (the inoculation amount is 1.0 multiplied by 10) according to the formula proportion7-3.0×1014And/g), and performing closed stacking fermentation (optionally performing closed stacking fermentation for 20d at 30 ℃) at normal temperature to obtain the active coal gangue mineral fertilizer.
The invention further comprises the step of adsorbing the compound microbial inoculum B3 by adopting a microorganism carrier to obtain a carrier-adsorbed compound microbial inoculum B3 before the step (3);
and (4) adding a carrier composite microbial inoculum B3#, uniformly stirring, and hermetically stacking and fermenting for 5-20 days at room temperature to obtain the active coal gangue nitrogen fixation mineral fertilizer. Specifically, the fermentation can be carried out for 10d in a closed stacking way at the temperature of 30 ℃.
The viable bacteria content of the compound microbial inoculum B1, the compound microbial inoculum B2 and the compound microbial inoculum B3 is 2x108-2x1014cfu/g。
The preparation method of the active coal gangue mineral fertilizer comprises the following steps of:
step (1), adding 5-10g of natural polymer plant adhesive, 5-10g of active coal gangue micropowder and 0.1-1g of water-soluble polymer thickener in sequence according to 1L of constant volume, adding water to 1L to prepare a coating agent solution, carrying out high-pressure sterilization, cooling to room temperature, adding a composite microbial inoculum B1, and fully mixing to obtain a mixed solution; specifically, the compound bacterial agent B1 is prepared into mixed bacterial liquid, and the weight percentage of the mixed bacterial liquid is as follows: coating agent 1: 4, adding the mixture into a coating agent in a volume ratio, and fully and uniformly mixing; the concentration of the mixed bacterial liquid is 1.0×107-6.0×1014/mL。
Step (2), under the aseptic operation condition, using an injector to transfer the mixed solution, and dropwise adding the mixed solution into a dispersion machine which is arranged on a magnetic stirrer and contains calcium chloride solution at a constant speed to obtain coated particles with the particle diameter of 2-3 mm;
standing and solidifying the coated particles at room temperature, and removing a calcium chloride solution; washing the coated particles with sterile water, specifically, after the coated particles are statically cured for 24 hours at room temperature, discarding the calcium chloride solution; washing the granules with sterile water for 2 times, transferring the granules into a known culture solution (culture medium: tryptone 10g, yeast extract 5g, NaCL10g, distilled water 1L, pH7.0-7.4), performing propagation culture for 72h, and washing the granules with sterile water; the molar concentration of the calcium chloride solution in the step is 0.1mol/L-0.4mol/L, and preferably 0.2 mol/L.
And (2) transferring the coated particles into a propagation culture solution for propagation culture for more than 24h, and washing the particles with sterile water to obtain the prepared coated microbial composite agent B1.
Based on the immobilized coating treatment of the compound microbial inoculum B1, the antagonistic action of the bacteria and other bacteria is mainly considered, the coal gangue is completely separated by adopting a plurality of bacteria, and the active coal gangue biological bacterial fertilizer is finally prepared, so the compatibility of the biological bacteria must be considered. The bacillus has excellent phosphate and potassium dissolving functions and strong organic phosphorus decomposing capacity. But the biocontrol strain with antagonistic effect on various pathogenic bacteria is easily infected by other bacteria, and the bacterial activity of the stock solution is reduced by 87.5 percent on day 8, 4 percent on day 15 and basically no bacterial activity on day 21 even if the stock solution is stored at 4 ℃. The immobilized cell coating is to fix microbial cells and enzymes in particles made of water-soluble polymers, and the internal microbial cells can proliferate in the particles.
The preparation method of the active coal gangue mineral fertilizer comprises the following steps of preparing a natural polymer adhesive, wherein the natural polymer adhesive is one or more than two of guar gum, xanthan gum, gellan gum, locust bean gum, arabic gum, chitin, chitosan, starch gum, CMC, HPMC, MC, sodium alginate, sodium humate and vegetable protein gum; the natural polymer adhesive is mostly cultured by pseudomonas in liquid culture medium such as saccharide, and the adhesive has compatibility with microorganism, can be used as a carrier of enzyme and microorganism, and can also be used as a gelatinizing agent in the microorganism culture medium instead of agar.
The water-soluble polymer thickener mainly comprises one or more than two of starch, cellulose, polyvinyl alcohol, polyacrylamide, potassium polyacrylate, sodium polyacrylate, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone and the like.
The preparation method of the active coal gangue mineral fertilizer comprises the following steps of: inoculating the compound microbial inoculum B3 into a liquid fermentation culture medium, and performing shake culture for more than 12h for activation; and (3) fermenting and culturing the activated mixed strain under the same condition to obtain a liquid microbial inoculum, putting the microbial carrier material and the liquid microbial inoculum into a magnetic dispersion machine with vacuum, and adsorbing at the normal temperature under the vacuum negative pressure to obtain a carrier adsorption composite microbial inoculum B3. In particular to a compound liquid microbial inoculum (the concentration is 1.0 multiplied by 10) prepared from a compound microbial inoculum B37-6.0×1014and/mL), inoculating the composite liquid microbial inoculum into a liquid fermentation culture medium according to the inoculation amount of 1.0-10%, and performing shaking culture at 30 ℃ and 180r/min for 24h for activation. The activated mixed strain is subjected to fermentation culture under the same conditions. According to the proportion of 1.0g-10g/mL of the microbial carrier material and the liquid microbial inoculum, putting the mixture into a magnetic dispersion machine with vacuum, and adsorbing for 2 hours at the normal temperature under the vacuum negative pressure of 0.05mpa so that the composite microbial inoculum enters the carrier.
According to the preparation method of the active coal gangue mineral fertilizer, the microbial carrier material is two or more than two of clinoptilolite powder, attapulgite, diatomite, bentonite, straw powder, bran, turf, porous ceramic, activated carbon, microporous glass, foam metal and the like.
The microbial vectors of the invention are based on consideration of the compatibility of the microbiota employed in the invention. And antagonism between flora. In addition, the heavy metal removal and nitrogen fixation are relatively long processes, and the heavy metal removal and nitrogen fixation are required throughout the whole process of preparing and using the fertilizer; in addition, the carrier requires loose and porous pores, huge surface area adsorption capacity, oxidation resistance, biological decomposition resistance or a large number of cavities and pore channels, has larger openness and internal surface area, and the microorganism immobilized by exchangeable alkali, alkaline earth metal cations and neutral water molecules has the advantages of easily controlled biological concentration, strong poison resistance, less strain loss, easily separated product, and immobilization of the microorganism by utilizing adsorption and charge effect when contacting with the microorganism; the support should have the following characteristics: (1) the carrier is inert to cells and is non-toxic to microorganisms; (2) the carrier activity is high, and the density of immobilized cells is high; (3) the mechanical strength and the chemical stability are good, and the microbial decomposition is resistant; (4) the operation is simple and convenient, and the molding is easy; (5) the diffusion resistance of the substrate and the product is small, and the mass transfer performance is good; (6) the recovery rate of the activity of the microorganism is high, and the microorganism can be used for a long time and repeatedly; (7) the raw materials are easy to obtain, and the cost is low.
The invention relates to a full-element efficient coal gangue biological bacterial fertilizer, which comprises the following raw materials in percentage by weight: 50% of animal waste, 40% of the active coal gangue nitrogen fixation mineral fertilizer, 9% of auxiliary materials prepared from wheat bran, rice chaff, straw powder or/and bacteria stick slag, 0.7% of urea or thiourea and 0.3% of conventional biological agent. The conventional biological agent in the embodiment of the invention can be selected from biological agents produced by Kangyuan oasis Biotechnology (Beijing) Co., Ltd, and the strains mainly comprise bacillus subtilis, bacillus licheniformis, saccharomyces cerevisiae and lactobacillus plantarum.
Mixing the above raw materials, directly piling on ground, generally forming trapezoid, height not more than 1.5 m, pile bottom width not more than 5m, and mixing with commercially available powdered organic fertilizer (viable bacteria content 2 × 10)10cfu/g)0.3 percent and water content of 50 percent, uniformly stirring the materials by layer, controlling the water content to be about 50 percent, carrying out aerobic fermentation for several days until the material temperature reaches 40-50 ℃ (generally 2-3 days in summer and about 5 days in spring and autumn), stacking and compacting, and carrying out anaerobic fermentation; and (3) turning over: because the temperature on the surface of the pile is different from that in the pile, the fermentation and decomposition degrees are different, and the pile should be inverted at proper time. The frequency of the pile-turning is determined by the temperature in the pile, generally starting from the pile-making and reaching 60-65 ℃; the temperature must be strictly controlled when the temperature in the stack exceeds 7 deg.CWhen the temperature is 0 ℃, indicating that the pile is lack of water, supplementing water in time, turning the pile, and continuing to ferment and thoroughly decompose; when the temperature in the pile is lower than 40 ℃, which indicates that the water in the pile is too high, the pile should be inverted to reduce the water, and the frequency of the pile inversion is not lower than 2 times. Fermentation time and temperature: the fermentation time is 7-10 days in spring and autumn, 5-7 days in summer and 15-20 days in winter. The most suitable environmental temperature for fermentation is 25-35 deg.C; and (5) completing the fermentation standard. The fermented compost has the flavor of koji but no odor, and the full-element high-efficiency coal gangue biological bacterial fertilizer is prepared.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention.
Example 1
Firstly, coal gangue is crushed into blocks with the size of 25mm by a special crusher. Adding 7.0 percent of industrial sugarcane sugar residues, 5.5 percent of humic acid, 0.5 percent of triethanolamine, 0.5 percent of ethylene glycol, 0.5 percent of sodium hexametaphosphate, 0.5 percent of lignin and 5 percent of urea into 80 percent of coal gangue. Adding into a well-known special mill, such as a ball mill, a Raymond mill, a vertical mill and the like, and grinding for 2 hours to obtain the coal gangue particles with surface activity, wherein the particle diameter of the coal gangue particles reaches 2000-3000 meshes. (taking YGM-Q4 European version of the high power mill as an example); CK (blank group, coal gangue), G1 (example 1-addition of additives-Industrial sugar cane bagasse 7.0%, humic acid 5.5%, triethanolamine 0.5%, ethylene glycol 0.5%, sodium hexametaphosphate 0.5%, lignin 0.5%, Urea 5%)
Figure BDA0002577291900000111
Figure BDA0002577291900000121
II, compound bacterial agent B1-1Immobilization coating treatment of
Adding 5g/L of the activated coal gangue powder into 5g/L of xanthan gum solution in sequence, adding 0.1g/L of polyoxyethylene aqueous solution to prepare a coating agent solution, sterilizing at high pressure, cooling to room temperature, and mixingSilicate bacteria and bacillus megatherium mixed bacterial liquid (the adding amount is 1: 1): coating agent 1: 4, adding the mixture into a coating agent in a volume ratio, and fully and uniformly mixing; transferring the mixed solution by using a sterile syringe, and dropwise adding the mixed solution into a dispersion machine which is arranged on a magnetic stirrer and contains 0.2mol/L calcium chloride solution at a constant speed to obtain particles with the particle diameter of 2-3 mm; standing and curing the coated particles at room temperature for 24h, and then removing the calcium chloride solution; cleaning the particles with sterile water for 2 times, transferring the particles into a known culture solution, performing propagation culture for 72h, washing the particles with sterile water to obtain the prepared coated microorganism composite microbial inoculum B1-1
(the mixed bacterial solution was stored at 4 ℃ C.; ph 7.0)
Figure BDA0002577291900000122
Figure BDA0002577291900000131
Third, compound bacteria liquid B1-2Selecting multiple Saccharomyces cerevisiae (effective viable count is 3.0 × 10)8Perml) and Aspergillus (effective viable count 2.5X 10)7Per mL) in a volume ratio of 2: 1 mixing and adding into active coal gangue according to the mixture ratio. The complex microbial inoculum is cultured according to a known method: after each microbial inoculum is separated and purified for a plurality of times, the microbial inoculum is activated once on a culture medium inclined plane, and mixed strains are prepared into a bacterial suspension on a known culture medium inclined plane.
(the mixed bacterial solution was stored at 4 ℃ C.; ph 7.0)
Figure BDA0002577291900000132
Activated coal gangue powder 965 of 2000-3000 meshes, humic acid 6, industrial sugar residue 4, urease (microbial growth factor) 3.0, polyphenol oxidase (microbial growth factor) 3.0, yeast extract (microbial growth factor) 3.0, urea 3.0 and potassium dihydrogen phosphate 2.0 are added into a dispersion machine to be uniformly mixed, the water content is adjusted to be 60 percent, the pH is adjusted to be 7-8, a coated microbial composite inoculum B1#5.0 is added into the mixture to be uniformly stirred,adding a compound microbial inoculum B2#4.0 according to the formula proportion, stacking and fermenting for 20d in a closed manner at the temperature of 30 ℃ to prepare the active coal gangue mineral fertilizer F1-1
(1) Active gangue mineral fertilizer F1-1Fertilizer efficiency index (CK is raw coal gangue)
Figure BDA0002577291900000133
Figure BDA0002577291900000141
(2) Active gangue mineral fertilizer F1-1Application contrast of
1) And test time: 05 months in 2017-10 months in 2017;
2) and a place: a phase change heat storage greenhouse vegetable base for a beautiful and beautiful road agricultural science and technology industrial park in Ningxia Yinchuan city.
3) And test design: the experiment is designed to be 2 treatments respectively, repeated for 3 times, and totally 6 experimental cells with the cell area of 30m2 are arranged randomly and are provided with protection rows.
CK, conventional fertilization, namely applying 100 kg/mu of compound fertilizer (N15-P15-K15) per mu, ridging after broadcasting, applying 10 kg/mu of water-soluble fertilizer (N20-P20-K20) after the 2 nd fruit setting of the eggplant and carrying out flushing application for 5 times till seedling pulling; k1: active gangue mineral fertilizer F1-1Partial substitution of chemical fertilizer, 50 kg/mu of common compound fertilizer (15-15) after applying in furrow, leveling land and furrow, active coal gangue F1-1Applying 1000kg of mineral fertilizer in holes per mu, and applying 10kg of water soluble fertilizer (N20-P20-K20) in holes per mu after the eggplants are set to fruit until the seedlings are pulled out, and applying 5 times in a flushing manner; other conditions are the same
F1-1Comparison of biomass parameters of round eggplant
Item CK (blank group) K1 Remarks to
Height cm of plant 11.1 12.8 The increase of the comparison is 15.3%
Neck thickness mm 2.08 2.53 The increase of the comparison is 21.6 percent
Maximum blade (c square meter) 7.7x6.2 8.1x6.7 The increase of the comparison is 13.7 percent
Blade extension cm 11.2 12.1 The increase of the comparison is 8.04 percent
Total number of 135 198 The increase of the comparison is 46.7 percent
Root length cm 11.9 12.6 The increase of the comparison is 5.9%
Yield (kg/mu) 2458 2796 The increase of the comparison is 13.8 percent
Fifthly, further proportioning the compound microbial inoculum B1-34 percent of mineral fertilizer F added with active coal gangue1-196 percent, and stacking and fermenting for 10 days in a closed way at the temperature of 30 ℃. Can prepare active coal gangue mineral fertilizer F1-2
(1) Composite bacterial agent B1-3Preparation: the mass-to-volume ratio of azotobacter chroococcum to leptospirillum ferrooxidans is 1: 2 preparing a compound liquid, inoculating the compound liquid microbial inoculum into a liquid fermentation culture medium according to the inoculation amount of 1%, and performing shaking culture at 30 ℃ and 180r/min for 24h for activation. The activated mixed strain is subjected to fermentation culture under the same conditions. According to the proportion of the microbial carrier clinoptilolite powder and the liquid microbial inoculum of 5g/mL, the mixture is put into a magnetic dispersion machine with vacuum, and the composite microbial inoculum enters the carrier after the mixture is adsorbed for 2 hours at the normal temperature under the vacuum negative pressure of 0.05 mpa.
(the mixed bacterial solution was stored at 4 ℃ C.; ph 7.0)
Figure BDA0002577291900000142
Figure BDA0002577291900000151
(2) Active gangue mineral nitrogen fixation fertilizer F1-2Fertilizer efficiency index (CK is raw coal gangue)
Figure BDA0002577291900000152
(3) Active gangue mineral nitrogen fixation fertilizer F1-2Application contrast of
1) And test time: 05 months in 2017-10 months in 2017;
2) and a place: a phase change heat storage greenhouse vegetable base for a beautiful and beautiful road agricultural science and technology industrial park in Ningxia Yinchuan city.
3) And test design: the experiment is designed to be 2 treatments respectively, repeated for 3 times, and totally 6 experimental cells with the cell area of 30m2 are arranged randomly and are provided with protection rows.
CK, conventional fertilization, namely applying 100 kg/mu of compound fertilizer (N15-P15-K15) per mu, ridging after broadcasting, applying 10 kg/mu of water-soluble fertilizer (N20-P20-K20) after the 2 nd fruit setting of the eggplant and carrying out flushing application for 5 times till seedling pulling; l1: active gangue mineral nitrogen fixation fertilizer F1-2Partial substitution of chemical fertilizer, 50 kg/mu of common compound fertilizer (15-15) after applying in furrow, leveling land and furrow, active coal gangue F1-2Applying 1000 kg/mu of mineral nitrogen-fixing fertilizer in a hole, and applying 10 kg/mu of water-soluble fertilizer (N20-P20-K20) after the eggplant bears fruit, and performing impact application for 5 times in total until seedling pulling; other conditions are the same
F1-2Comparison of biomass parameters of round eggplant
Item CK (blank group) L1 Remarks to
Average plant height cm 11.1 13.82 The increase of the comparison is 24.50 percent
Average neck thickness mm 2.08 2.66 The increase of the comparison is 27.88%
Maximum leafSheet (C square meter) 7.7x6.2 7.9x7.0 The increase of the comparison is 15.8%
Blade extension cm 11.2 12.2 The increase of the comparison is 8.9 percent
Total number of 135 200 Increase of 48.2% in the control
Root length cm 11.9 12.7 The increase of the comparison is 11.1%
Yield (kg/mu) 2458 2799 The increase of the comparison is 13.9 percent
Sixthly, the active coal gangue nitrogen fixation mineral fertilizer F is further prepared1-2Preparation of full-element efficient gangue biological bacterial fertilizer F1-3. The raw materials by weight percentage: 50% of cow dung, 40% of active coal gangue mineral fertilizer F2#, 9% of bran, 0.7% of urea or thiourea, and a commercially available powdery organic fertilizer microbial inoculum (with viable bacteria content of 2x 10)10cfu/g)0.3 percent and water content of 50 percent; preparing the full-element high-efficiency gangue biological bacterial fertilizer F according to the method 2.61-3
(1) Full-element efficient gangue biological bacterial fertilizer F1-3(powder) Performance index
Figure BDA0002577291900000161
Figure BDA0002577291900000171
(2) Full-element efficient gangue biological bacterial fertilizer F1-3(powder) fertilizer efficiency field test
1) And test time: 05 months in 2017-10 months in 2017;
2) and a place: a phase change heat storage greenhouse vegetable base for a beautiful and beautiful road agricultural science and technology industrial park in Ningxia Yinchuan city.
3) And test design: the test is respectively designed with 4 treatments and 3 times of repetition, and totally 12 test cells with the cell area of 30m2 are arranged randomly and are provided with protection rows.
4) And test treatment: CK, no fertilization (blank control); s1-1: applying fertilizer conventionally, applying 100 kg/mu of compound fertilizer (N15-P15-K15) per mu, ridging after spreading, applying 10 kg/mu of water-soluble fertilizer (N20-P20-K20) after the second ear of the cucumber is fruited and the fruit is set, and applying 10 times by flushing until pulling seedlings; s1-2: the full-element efficient coal gangue biological bacterial fertilizer F3 (powder) completely replaces the fertilizer, and the full-element efficient coal gangue biological bacterial fertilizer F1-31000 kg/mu (powder), hole application, no additional application of any fertilizer in the whole growth period; s1-3: full-element efficient gangue biological bacterial fertilizer F1-3The fertilizer is partially replaced by the (powder), common compound fertilizer (15-15) 50 kg/mu is applied in furrow and then is leveled and ridged, bio-organic fertilizer 500 kg/mu is applied in holes, water soluble fertilizer (N20-P20-K20)10 kg/mu is applied after the second ear fruit of cucumber is set, and the fertilizer is applied by flushing for 5 times until seedling pulling; other field management measures are the same.
Influence of different fertilization schemes on cucumber growth index (mean value)
Figure BDA0002577291900000172
Figure BDA0002577291900000181
Influence of different fertilization schemes on cucumber economic benefits (mean value)
Figure BDA0002577291900000182
Note: 3000 yuan/ton of compound fertilizer and 700 yuan/ton of F3; the average cucumber price is 1.5 yuan/jin
Example 2
Firstly, coal gangue is crushed into blocks with the size of 25mm by a special crusher. Adding 6.0 percent of industrial beet sugar manufacturing waste liquid, 1.5 percent of citric acid, 0.2 percent of tri-isopropanolamine, 0.3 percent of xylitol, 0.5 percent of sodium tripolyphosphate, 3.5 percent of paper mill waste liquid and 3.0 percent of calcium phosphate into 85 percent of coal gangue. Adding into a well-known special mill, such as a ball mill, a Raymond mill, a vertical mill, and the like, and grinding for 2-4 hours to obtain the coal gangue particles with surface activity, wherein the particle size of the coal gangue particles reaches 2000-3000 meshes. (taking YGM-Q4 European edition strong flour mill as an example)
Figure BDA0002577291900000183
Figure BDA0002577291900000191
Figure BDA0002577291900000201
II, compound bacterial agent B2-1Immobilization coating treatment of
Preparing 1L of aqueous solution according to 10g/L of starch, sequentially adding 10g of the activated coal gangue powder and 1g of polyvinyl alcohol aqueous solution to prepare a coating agent solution, sterilizing at high pressure, cooling to room temperature, and mixing the following bacteria solutions according to the ratio of bacillus laterosporus to bacillus amyloliquefaciens (the inoculation amount is 1: 1): coating agent 1: 4, adding the mixture into a coating agent in a volume ratio, and fully and uniformly mixing; transferring the mixed solution by using a sterile syringe, and dropwise adding the mixed solution into a dispersion machine which is arranged on a magnetic stirrer and contains 0.2mol/L calcium chloride solution at a constant speed to obtain particles with the particle diameter of 2-3 mm;standing and curing the coated particles at room temperature for 24h, and then removing the calcium chloride solution; cleaning the particles with sterile water for 2 times, transferring the particles into a known culture solution, performing propagation culture for 72h, washing the particles with sterile water to obtain the prepared coated microorganism composite microbial inoculum B2-1(the mixed bacterial solution was stored at 4 ℃ C.; pH 7.0).
Figure BDA0002577291900000202
Figure BDA0002577291900000211
Third, compound bacteria liquid B2-2Selecting Lactobacillus casei (effective viable count is 2.0 × 10)8Perml) and Flavobacterium (effective viable count 4.5X 107Per mL) in a volume ratio of 3: 1 mixing and adding into active coal gangue according to the mixture ratio. The complex microbial inoculum is cultured according to a known method: after each microbial inoculum is separated and purified for a plurality of times, the microbial inoculum is activated once on a culture medium inclined plane, and mixed strains are prepared into a bacterial suspension on a known culture medium inclined plane.
(the mixed bacterial solution was stored at 4 ℃ C.; pH 7.0)
Figure BDA0002577291900000212
Adding activated coal gangue powder 980 with meshes of 2000-3000, citric acid 3.0, industrial beet sugar-making waste liquor 4.0, cellulase (microbial growth factor) 0.5, proteinase (microbial growth factor) 0.5, peptone 2.0, urea 3.0 and potassium dihydrogen phosphate 2.0 into a dispersion machine, uniformly mixing, regulating water content to 60%, regulating pH to 7-8, and coating microbial composite bacteria B2-1#3.0, adding into the mixture, stirring, and adding into the complex microbial inoculum B according to the formula proportion2-2#2.0 sealed stacking fermentation at 30 deg.C for 20d to obtain active coal gangue mineral fertilizer F2-1
(1) Active gangue mineral fertilizer F2-1Fertilizer efficiency index (CK is raw coal gangue)
Figure BDA0002577291900000213
(2) Active gangue mineral fertilizer F2-1Application contrast of
1) And test time: 05 months in 2017-10 months in 2017;
2) and a place: a phase change heat storage greenhouse vegetable base for a beautiful and beautiful road agricultural science and technology industrial park in Ningxia Yinchuan city.
3) And test design: the experiment respectively designs 2 treatments, 3 times of repetition, and totally 6 experimental cells with the cell area of 30m2The cells are randomly arranged and provided with protection rows.
CK, conventional fertilization, namely applying 100 kg/mu of compound fertilizer (N15-P15-K15) per mu, ridging after broadcasting, applying 10 kg/mu of water-soluble fertilizer (N20-P20-K20) after the 2 nd fruit setting of the eggplant and carrying out flushing application for 5 times till seedling pulling; k2: active gangue mineral fertilizer F2-1Partial substitution of chemical fertilizer, 50 kg/mu of common compound fertilizer (15-15) after applying in furrow, leveling land and furrow, active coal gangue F2-1Applying 1000kg of mineral fertilizer in holes per mu, and applying 10kg of water soluble fertilizer (N20-P20-K20) in holes per mu after the eggplants are set to fruit until the seedlings are pulled out, and applying 5 times in a flushing manner; other field management measures are the same
F2-1Comparison of biomass parameters of round eggplant
Item CK (blank group) K2 Remarks to
Height cm of plant 11.1 12.16 ControlThe increase is 14.54 percent
Neck thickness mm 2.08 2.40 The increase of the comparison is 20.52 percent
Maximum blade (c square meter) 7.7x6.2 7.7x7.0 The increase of the comparison is 12.90 percent
Blade extension cm 11.2 11.50 The increase of the comparison is 7.64 percent
Total number of 135 188.10 The increase of the comparison is 44.37%
Root length cm 11.9 11.97 The increase of the comparison is 5.61 percent
Yield (kg/mu) 2458 2740 The increase of the comparison is 13.52 percent
Fifthly, further proportioning the compound microbial inoculum B2-38 percent of mineral fertilizer F added with active coal gangue2-192% by weight, and is dense at 30 DEG CAnd (5) closing and stacking for fermentation for 10 d. Can prepare active coal gangue mineral fertilizer F2-2
(1) Composite bacterial agent B2-3Preparation: the mass-to-volume ratio of the azospirillum lipogenes to the thiobacillus caldus is 1: 1, preparing a composite liquid, inoculating the composite liquid microbial inoculum into a liquid fermentation culture medium according to the inoculation amount of 1%, and performing shaking culture at 30 ℃ and 180r/min for 24h for activation. The activated mixed strain is subjected to fermentation culture under the same conditions. According to the proportion of the microorganism carrier attapulgite and the liquid microbial inoculum of 10g/mL, putting the microorganism carrier attapulgite and the liquid microbial inoculum into a magnetic dispersion machine with vacuum, and adsorbing for 2 hours at the normal temperature under the vacuum negative pressure of 0.05mpa to ensure that the composite microbial inoculum enters the carrier.
(the mixed bacterial solution was stored at 4 ℃ C.; pH 7.0)
Figure BDA0002577291900000221
(2) Active gangue mineral nitrogen fixation fertilizer F2-2Fertilizer efficiency index (CK is raw coal gangue)
Figure BDA0002577291900000231
(3) Active gangue mineral nitrogen fixation fertilizer F2-2Application contrast of
1) And test time: 05 months in 2017-10 months in 2017;
2) and a place: a phase change heat storage greenhouse vegetable base for a beautiful and beautiful road agricultural science and technology industrial park in Ningxia Yinchuan city.
3) And test design: the experiment is designed to be 2 treatments respectively, repeated for 3 times, and totally 6 experimental cells with the cell area of 30m2 are arranged randomly and are provided with protection rows.
CK, conventional fertilization, namely applying 100kg of compound fertilizer (N15-P15-K15) per mu, ridging after spreading, and applying water-soluble fertilizer (N) after the eggplant bears fruit at the 2 nd day20-P20-K20)10 kg/mu, and 5 times of flushing application in total until seedling pulling; k2: full-element efficient gangue biological bacterial fertilizer F2-2The fertilizer is partially replaced by the powder, after 50 kg/mu of furrow application of common compound fertilizer (15-15), flat ground and furrow application are carried out, 500 kg/mu of hole application of biological organic fertilizer is carried out, and when the fruit of the 2 nd ear of cucumber is plantedTopdressing water soluble fertilizer (N) after fruit setting20-P20-K20)10 kg/mu, and 5 times of flushing application in total until seedling pulling; other field management measures are under the same conditions.
F2-2Comparison of biomass parameters of round eggplant
Item CK (blank group) K2 Remarks to
Average plant height cm 11.1 13.13 The increase of the comparison is 23.30 percent
Average neck thickness mm 2.08 2.53 The increase of the comparison is 26.50%
Maximum blade (c square meter) 7.7x6.2 7.9x6.7 The increase of the comparison is 15.01 percent
Blade extension cm 11.2 11.59 The increase of the comparison is 8.46 percent
Total number of 135 197 The increase of the comparison is 47.50%
Root length cm 11.9 12.1 The increase of the comparison is 10.55 percent
Yield (kg/mu) 2458 2659 The increase of the comparison is 13.21 percent
Sixthly, the active coal gangue nitrogen fixation mineral fertilizer F is further prepared2-2Preparation of full-element efficient gangue biological bacterial fertilizer F2-3. The raw materials by weight percentage: 50% of pig manure and active coal gangue mineral fertilizer F2-240 percent of wheat bran 9 percent, 0.7 percent of urea or thiourea, and a commercially available powdery organic fertilizer microbial inoculum (viable bacteria content is 2x 10)10cfu/g)0.3 percent and water content of 50 percent; preparing the full-element high-efficiency gangue biological bacterial fertilizer F according to the method 2.62-3
(1) Full-element efficient gangue biological bacterial fertilizer F2-3(powder) Performance index
Figure BDA0002577291900000241
Figure BDA0002577291900000251
(2) Full-element efficient gangue biological bacterial fertilizer F2-3(powder) fertilizer efficiency field test
1) And test time: 05 months in 2017-10 months in 2017;
2) and a place: a phase change heat storage greenhouse vegetable base for a beautiful and beautiful road agricultural science and technology industrial park in Ningxia Yinchuan city.
3) And test design: the test is respectively designed with 4 treatments and 3 times of repetition, and totally 12 test cells with the cell area of 30m2 are arranged randomly and are provided with protection rows.
4) And test treatment: CK, no fertilization (blank control); s2-1: applying fertilizer conventionally, applying 100 kg/mu of compound fertilizer (N15-P15-K15) per mu, ridging after spreading, applying 10 kg/mu of water-soluble fertilizer (N20-P20-K20) after the second ear of the cucumber is fruited and the fruit is set, and applying 10 times by flushing until pulling seedlings; s2-2: full-element efficient gangue biological bacterial fertilizer F2-3(powder) completely replaces chemical fertilizer, and is a full-element high-efficiency coal gangue biological bacterial fertilizer F2-31000 kg/mu (powder), hole application, no additional application of any fertilizer in the whole growth period; s2-3: full-element efficient gangue biological bacterial fertilizer F2-3The fertilizer is partially replaced by the powder, 50 kg/mu of common compound fertilizer (15-15) is applied in furrow and then is leveled and ridged, 500 kg/mu of bio-organic fertilizer is applied in holes, and water soluble fertilizer (N) is applied after the fruit of the 2 nd cluster of cucumber is set20-P20-K20)10 kg/mu, and 5 times of flushing application in total until seedling pulling; other field management measures are the same.
Influence of different fertilization schemes on cucumber growth index (mean value)
Fertilization scheme 42d plant height (cm) 40d Stem thickness (mm) Weight of single fruit (g) Yield (jin/mu)
CK 67.1 6.30 158.6 3872.57
S2-1 88.50 8.8 201.4 12900.0
S2-2 98.05 8.84 210.01 14435.40
S2-3 94.19 8.60 202.8 13565.20
Influence of different fertilization schemes on cucumber economic benefits (mean value)
Figure BDA0002577291900000252
Figure BDA0002577291900000261
Note: 3000 yuan/ton of compound fertilizer and 700 yuan/ton of F3; the average cucumber price is 1.5 yuan/jin
Example 3
Firstly, coal gangue is crushed into blocks with the size of 25mm by a special crusher. Adding molasses 3.0%, polycarboxylic acid 1.0%, diethanolamine 0.2%, glycerol 0.5%, sodium pyrophosphate 0.3%, sodium lignosulfonate 3.0% and borax 2.0% into 90% coal gangue. Adding into a well-known special mill, such as a ball mill, a Raymond mill, a vertical mill, and the like, and grinding for 2-4 hours to obtain the coal gangue particles with surface activity, wherein the particle size of the coal gangue particles reaches 2000-3000 meshes. (taking YGM-Q4 European edition strong flour mill as an example)
Figure BDA0002577291900000262
Figure BDA0002577291900000271
Figure BDA0002577291900000281
II, compound bacterial agent B3-1Immobilization coating treatment of
Preparing 1L of aqueous solution according to 8g/L of starch, sequentially adding 7g of the activated coal gangue powder and 2g of polyvinylpyrrolidone to prepare a coating agent solution, carrying out high-pressure sterilization, cooling to room temperature, and mixing the following bacteria solutions according to the ratio of the bacillus laterosporus to the bacillus circulans (the inoculation amount is 1: 1): coating agent 1: 4, adding the mixture into a coating agent in a volume ratio, and fully and uniformly mixing; transferring the mixed solution by using a sterile syringe, and dropwise adding the mixed solution into a dispersion machine which is arranged on a magnetic stirrer and contains 0.2mol/L calcium chloride solution at a constant speed to obtain particles with the particle diameter of 2-3 mm; standing and curing the coated particles at room temperature for 24h, and then removing the calcium chloride solution; cleaning the particles with sterile water for 2 times, transferring the particles into a known culture solution, performing propagation culture for 72h, washing the particles with sterile water to obtain the prepared coated microorganism composite microbial inoculum B3-1
(the mixed bacterial solution was stored at 4 ℃ C.; pH 7.0)
Figure BDA0002577291900000282
Third, compound bacteria liquid B3-3Selecting pseudomonas (the effective viable count is 3.0 multiplied by 10)8Perml) and Trichoderma (effective viable count 1.0X 107Per mL) in a volume ratio of 1.5: 1 mixing and adding into active coal gangue according to the mixture ratio. The complex microbial inoculum is cultured according to a known method: after each microbial inoculum is separated and purified for a plurality of times, the microbial inoculum is activated once on a culture medium inclined plane, and mixed strains are prepared into a bacterial suspension on a known culture medium inclined plane.
(the mixed bacterial solution was stored at 4 ℃ C.; pH 7.0)
Figure BDA0002577291900000291
4. Adding activated coal gangue powder 960 of 2000-3000 meshes, molasses 10.0, polycarboxylic acid 6.0, catalase (microbial growth factor) 2.50, neutral protease (microbial growth factor) 2.50, amino acid 5.0, urea 3.0 and potassium dihydrogen phosphate 2.0 into a dispersion machine, uniformly mixing, adjusting the water content to 60%, adjusting the pH to 7-8, and adding a coated microbial composite bacterial agent B3-1#4.0, adding into the mixture, stirring, and adding into the complex microbial inoculum B according to the formula proportion3-2#5.0 sealed stacking fermentation at 30 ℃ for 20d to prepare the active coal gangue mineral fertilizer F3-1
(1) Active gangue mineral fertilizer F3-1Fertilizer efficiency index (CK is raw coal gangue)
Figure BDA0002577291900000292
(2) Active gangue mineral fertilizer F3-1Application contrast of
1) And test time: 05 months in 2017-10 months in 2017;
2) and a place: a phase change heat storage greenhouse vegetable base for a beautiful and beautiful road agricultural science and technology industrial park in Ningxia Yinchuan city.
3) And test design: the experiment is designed to be 2 treatments respectively, repeated for 3 times, and totally 6 experimental cells with the cell area of 30m2 are arranged randomly and are provided with protection rows.
CK, conventional fertilization, 100 kg/mu of compound fertilizer (N15-P15-K15) is applied per mu, and the fertilizer is applied after the fertilizer is spreadLong, applying water soluble fertilizer (N) after the 2 nd fruit setting of eggplant20-P20-K20)10 kg/mu, and 5 times of flushing application in total until seedling pulling; k3: active gangue mineral fertilizer F3-1Partial substitution of chemical fertilizer, 50 kg/mu of common compound fertilizer (15-15) after applying in furrow, leveling land and furrow, active coal gangue F3-1Applying 1000 kg/mu mineral fertilizer in holes, and applying water soluble fertilizer (N) after the eggplant bears fruit20-P20-K20)10 kg/mu, and 5 times of flushing application in total until seedling pulling; other field management measures are the same
F3-1Comparison of biomass parameters of round eggplant
Item CK (blank group) K3 Remarks to
Height cm of plant 11.1 12.04 The increase of the comparison is 14.40 percent
Neck thickness mm 2.08 2.39 The increase of the comparison is 20.50 percent
Maximum blade (c square meter) 7.7x6.2 7.7x6.9 The increase of the comparison is 12.64 percent
Blade extension cm 11.2 11.27 The increase of the comparison is 7.48 percent
Total number of 135 180.60 The increase of the comparison is 42.60 percent
Root length cm 11.9 11.49 The increase of the comparison is 5.39%
Yield (kg/mu) 2458 2703 The increase of the comparison is 13.45 percent
Fifthly, further proportioning the compound microbial inoculum B3-32 percent of mineral fertilizer F added with active coal gangue3-198 percent, and stacking and fermenting for 10 days in a closed way at the temperature of 30 ℃. Can prepare active coal gangue mineral fertilizer F3-2
(1) Composite bacterial agent B2-3Preparation: the mass-to-volume ratio of azotobacter bailii to acidithiobacillus ferrooxidans is 1: 1, preparing a composite liquid, inoculating the composite liquid microbial inoculum into a liquid fermentation culture medium according to the inoculation amount of 1%, and performing shaking culture at 30 ℃ and 180r/min for 24h for activation. The activated mixed strain is subjected to fermentation culture under the same conditions. According to the proportion of the microbial carrier diatomite and the liquid microbial inoculum of 10g/mL, putting the microbial carrier diatomite and the liquid microbial inoculum into a magnetic dispersion machine with vacuum, and adsorbing for 2 hours at the normal temperature under the vacuum negative pressure of 0.05mpa to ensure that the composite microbial inoculum enters the carrier. (the mixed bacterial solution was stored at 4 ℃ C.; pH 7.0)
Figure BDA0002577291900000301
(2) Active gangue mineral nitrogen fixation fertilizer F3-3Fertilizer efficiency index (CK is raw coal gangue)
Figure BDA0002577291900000302
Figure BDA0002577291900000311
(3) Active gangue mineral nitrogen fixation fertilizer F3-3Application contrast of
1) And test time: 05 months in 2017-10 months in 2017;
2) and a place: a phase change heat storage greenhouse vegetable base for a beautiful and beautiful road agricultural science and technology industrial park in Ningxia Yinchuan city.
3) And test design: the experiment is designed to be 2 treatments respectively, repeated for 3 times, and totally 6 experimental cells with the cell area of 30m2 are arranged randomly and are provided with protection rows.
CK, conventional fertilization, namely applying 100 kg/mu of compound fertilizer (N15-P15-K15) per mu, ridging after broadcasting, applying 10 kg/mu of water-soluble fertilizer (N20-P20-K20) after the 2 nd fruit setting of the eggplant and carrying out flushing application for 5 times till seedling pulling; k3: full-element efficient gangue biological bacterial fertilizer F3-3The fertilizer is partially replaced by the (powder), common compound fertilizer (15-15) 50 kg/mu is applied in furrow and then is leveled and ridged, bio-organic fertilizer 500 kg/mu is applied in holes, water soluble fertilizer (N20-P20-K20)10 kg/mu is applied after the second ear fruit of cucumber is set, and the fertilizer is applied by flushing for 5 times until seedling pulling; other field management measures are under the same conditions;
F3-3comparison of biomass parameters of round eggplant
Figure BDA0002577291900000312
Figure BDA0002577291900000321
Sixthly, the active coal gangue nitrogen fixation mineral fertilizer F is further prepared3-2Preparation of full-element efficient gangue biological bacterial fertilizer F3-3. The raw materials by weight percentage: 50% of chicken manure and active coal gangue mineral fertilizer F3-240 percent of wheat bran 9 percent, 0.7 percent of urea or thiourea, and a commercially available powdery organic fertilizer microbial inoculum (viable bacteria content is 2x 10)10cfu/g)0.3 percent and water content of 55 percent; preparing the full-element high-efficiency gangue biological bacterial fertilizer F according to the method 2.63-3
(1) Full-element efficient gangue biological bacterial fertilizer F3-3(powder) Performance index
Figure BDA0002577291900000322
Figure BDA0002577291900000331
(2) Full-element efficient gangue biological bacterial fertilizer F2-3(powder) fertilizer efficiency field test
1) And test time: 05 months in 2017-10 months in 2017;
2) and a place: a phase change heat storage greenhouse vegetable base for a beautiful and beautiful road agricultural science and technology industrial park in Ningxia Yinchuan city.
3) And test design: the experiment respectively designs 4 treatments, 3 times of repetition, and totally 12 experimental cells with the cell area of 30m2The cells are randomly arranged and provided with protection rows.
4) And test treatment: CK, no fertilization (blank control); s3-1: applying fertilizer conventionally, applying 100 kg/mu of compound fertilizer (N15-P15-K15) per mu, ridging after spreading, applying 10 kg/mu of water-soluble fertilizer (N20-P20-K20) after the second ear of the cucumber is fruited and the fruit is set, and applying 10 times by flushing until pulling seedlings; s3-2: full-element efficient gangue biological bacterial fertilizer F2-3(powder) completely replaces chemical fertilizer, and is a full-element high-efficiency coal gangue biological bacterial fertilizer F3-31000 kg/mu (powder), hole application, no additional application of any fertilizer in the whole growth period; s3-3: full-element efficient gangue biological bacterial fertilizer F3-3(powder) partial substitution of chemical fertilizer, ordinary compoundingApplying 50kg of fertilizer (15-15) in a furrow, leveling land, applying 500kg of bio-organic fertilizer in a hole per mu, applying 10kg of water-soluble fertilizer (N20-P20-K20) in 10kg per mu after the second cluster fruit of the cucumber is set, and performing impact application for 5 times in total until seedling pulling; other field management measures are the same.
Influence of different fertilization schemes on cucumber growth index (mean value)
Fertilization scheme 42d plant height (cm) 40d Stem thickness (mm) Weight of single fruit (g) Yield (jin/mu)
CK 67.1 6.30 158.6 3872.57
S3-1 88.50 8.8 201.4 12900.0
S3-2 98.34 8.88 211.69 14565.32
S3-3 94.57 8.63 204.43 13673.72
Influence of different fertilization schemes on cucumber economic benefits (mean value)
Figure BDA0002577291900000332
Note: 3000 yuan/ton of compound fertilizer and 700 yuan/ton of F3; the average cucumber price is 1.5 yuan/jin
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (20)

1. The active coal gangue micro powder is characterized in that the active coal gangue micro powder is obtained by mixing and grinding the following raw materials: 80 to 90 percent of coal gangue, 1.0 to 10.0 percent of sugar industry waste residue, 1.0 to 10.0 percent of organic acid, 0.5 to 3.0 percent of alkanolamine substance, 0.4 to 4.0 percent of polar additive, 0.5 to 3.0 percent of dispersant, 0.5 to 3.0 percent of surfactant and 1.0 to 10.0 percent of excitant.
2. The active coal gangue micropowder of claim 1, wherein the coal gangue is crushed into blocks with the size of less than or equal to 50mm by a crusher; the particle size of the micro powder reaches 2000-3000 meshes.
3. The activated coal gangue micropowder of claim 1, wherein the organic acid is one or more of malic acid, oxalic acid, citric acid, humic acid, acrylic acid, polyacrylic acid, polycarboxylic acid, maleic anhydride, acetic acid, and benzoic acid.
4. The activated coal gangue micropowder of claim 1, wherein the alkanolamine is one or more selected from monoethanolamine, dipropanolamine, tripropanolamine, dibutanolamine, tributanolamine, triethanolamine, diethanolamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, 2-dihydroxy dipropylamine, triethanolamine disulfonate, polyacrylamide and potassium polyacrylate.
5. The active coal gangue micropowder of claim 1, wherein the industrial waste residue for sugar production is one or more of molasses, sugar residue, calcium sugar, bagasse, beet pulp waste, syrup, pulp waste, corn syrup, lactose, glucose or glucoside.
6. The activated coal gangue micropowder of claim 1, wherein the polar additive is one or more of xylitol, diethylene glycol, propylene glycol, glycerol, ethylene glycol, diethylene glycol, sorbitol, sodium gluconate, sodium glycolate and sodium citrate.
7. The activated coal gangue micropowder of claim 1, wherein the excitant is one or more than two of ammonium nitrate, citric acid residue, urea, calcium phosphate, calcium nitrate, potassium carbonate, monopotassium phosphate, calcium phosphate residue, potassium sulfate, potassium sulfite, calcium sulfite, zinc sulfate, borax, molybdenum sulfate, copper sulfate, ferric sulfate and EDTA.
8. The activated coal gangue micropowder of claim 1, wherein the dispersant is one or more of trisodium phosphate, sodium hexametaphosphate, sodium tripolyphosphate, sodium gluconate, sodium pyrophosphate, sodium citrate, sodium humate, sodium fulvate, and sodium dihydrogen phosphate.
9. The activated coal gangue micropowder of claim 1, wherein the surfactant is one or more of sodium dodecylbenzene sulfonate, lignin, sodium lignosulfonate, calcium lignosulfonate and paper mill waste liquid.
10. The active coal gangue mineral fertilizer is characterized by comprising the following raw materials in parts by weight: the active coal gangue micropowder 960-980 parts, the organic acid 1-10 parts, the industrial waste residue 1-10 parts, the composite microbial inoculum B10.5-5 parts, the composite microbial inoculum B20.4-4 parts, the microorganism growth factor 3-10 parts, the urea 0.3 part and the monopotassium phosphate 0.2 part as defined in any one of claims 1 to 9.
11. The active coal gangue mineral fertilizer of claim 10, further comprising 32-8 parts of a complex microbial inoculum B.
12. The active coal gangue mineral fertilizer as claimed in claim 11, wherein the complex microbial agent B1 is a mixed bacteria of two or more of Bacillus megaterium, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus subtilis, Bacillus thuringiensis, Bacillus badius, silicate bacteria, Bacillus mucilaginosus, Bacillus atrophaeus, Bacillus circulans and Bacillus laterosporus with phosphate and potassium solubilizing functions; the composite microbial inoculum B2 is a mixed bacterium of two or more than two of saccharomyces cerevisiae, pseudomonas, lactobacillus casei, aspergillus, trichoderma, achromobacter, rhizopus, flavobacterium, proteus, serratia, arthrobacter or streptomyces; the compound microbial inoculum B3 is azotobacter chroococcum, azospirillum lipolyticum, bradyrhizobium nodorum, nitrorhizobium rhizobium stemorum, mesorhizobium baiviense, azospirillum brasiliensis, azotobacter bailii, azotobacter vinelandii, azotobacter paspalum, azotobacter indicum; two or more of Acidithiobacillus caldus, leptospirillum ferrooxidans, thermoferritin phaga, Acidithiobacillus ferrooxidans, Candida, Acidithiobacillus thiooxidans or Acidithiobacillus thiooxidans.
13. The active coal gangue mineral fertilizer of claim 11, wherein the microbial growth factor comprises a biological enzyme and a nutrient, and the mass ratio of the biological enzyme to the nutrient is 0.5: 1-2: 1; the nutrient substances comprise more than two of vitamins, amino acids, basic groups, porphyrin and derivatives thereof, sterol, amines, yeast extract, peptone, malt extract or corn steep liquor; the biological enzyme is any two of catalase, laccase, urease, neutral protease, polyphenol oxidase, phytase, cellulase, xylanase, protease and pectinase; the activity of the biological enzyme is 0.5-10 ten thousand u/g.
14. A preparation method of an active coal gangue mineral fertilizer, which is characterized in that,
step (1), weighing raw materials of the active coal gangue mineral fertilizer according to the claims 11 to 13;
step (2), carrying out immobilization coating treatment on the compound microbial inoculum B1 to obtain a coated microorganism compound microbial inoculum B1;
and (3) adding active coal gangue micro powder, organic acid, industrial waste residues, microbial growth factors, urea and potassium dihydrogen phosphate into a dispersion machine according to the mass ratio, uniformly mixing, adjusting the water content to 50-65%, adjusting the pH value to 7-8, adding a coated microbial compound agent B1 into the mixture, uniformly stirring, adding a compound agent B2 according to the formula proportion, and hermetically stacking and fermenting at normal temperature to obtain the active coal gangue mineral fertilizer.
15. The preparation method of the active coal gangue mineral fertilizer as claimed in claim 13, wherein before the step (3), the method further comprises the steps of carrying out adsorption treatment on the complex microbial inoculum B3 by adopting a microbial carrier to obtain a carrier adsorption complex microbial inoculum B3; and (4) adding a carrier composite microbial inoculum B3#, uniformly stirring, and hermetically stacking and fermenting for 5-20 days at room temperature to obtain the active coal gangue nitrogen fixation mineral fertilizer.
16. The preparation method of the active coal gangue mineral fertilizer as claimed in claim 13, wherein the immobilized coating treatment of the complex microbial agent B1 specifically comprises the following steps:
step (1), adding 5-10g of natural polymer plant adhesive and 5-10g of natural polymer plant adhesive according to 1L of constant volume in sequence
Adding active coal gangue micropowder and 0.1-1g of water-soluble polymer thickener to 1L to prepare a coating agent solution, sterilizing at high pressure, cooling to room temperature, adding a composite microbial agent B1, and fully mixing to obtain a mixed solution;
step (2), under the aseptic operation condition, using an injector to transfer the mixed solution, and dropwise adding the mixed solution into a dispersion machine which is arranged on a magnetic stirrer and contains calcium chloride solution at a constant speed to obtain coated particles with the particle diameter of 2-3 mm; standing and solidifying the coated particles at room temperature, and removing a calcium chloride solution; washing the coated particles with sterile water;
and (2) transferring the coated particles into a propagation culture solution for propagation culture for more than 24h, and washing the particles with sterile water to obtain the prepared coated microbial composite agent B1.
17. The method for preparing the active coal gangue mineral fertilizer as claimed in claim 14, wherein the natural polymer adhesive is one or more than two of guar gum, xanthan gum, gellan gum, locust bean gum, gum arabic, chitin, chitosan, starch gum, CMC, HPMC, MC, sodium alginate, sodium humate and vegetable protein gum; the water-soluble polymer thickener mainly comprises one or more than two of starch, cellulose, polyvinyl alcohol, polyacrylamide, potassium polyacrylate, sodium polyacrylate, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone and the like.
18. The preparation method of the active coal gangue mineral fertilizer as claimed in any one of claims 13 to 15, wherein the carrier adsorption complex microbial agent B3 is obtained by the following steps: inoculating the compound microbial inoculum B3 into a liquid fermentation culture medium, and performing shake culture for more than 12h for activation; and (3) fermenting and culturing the activated mixed strain under the same condition to obtain a liquid microbial inoculum, putting the microbial carrier material and the liquid microbial inoculum into a magnetic dispersion machine with vacuum, and adsorbing at the normal temperature under the vacuum negative pressure to obtain a carrier adsorption composite microbial inoculum B3.
19. The method for preparing the active coal gangue mineral fertilizer as claimed in claim 16, wherein the microorganism carrier material is two or more of clinoptilolite powder, attapulgite, diatomite, bentonite, straw powder, chaff, turf, porous ceramic, activated carbon, microporous glass, foam metal and the like.
20. The full-element efficient coal gangue biological bacterial fertilizer is characterized by comprising the following raw materials in percentage by weight: 50% of animal waste, 40% of the active coal gangue mineral fertilizer prepared by any one of claims 10 to 17 or the active coal gangue mineral fertilizer prepared by the preparation method, 9% of auxiliary materials prepared from wheat bran, rice chaff, straw powder or/and mushroom stick slag, 0.7% of urea or thiourea and 0.3% of conventional biological fermentation inoculum.
CN202010657574.1A 2020-07-09 2020-07-09 Active coal gangue micro powder, active coal gangue mineral fertilizer and preparation method Pending CN111792952A (en)

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CN112028709A (en) * 2020-08-06 2020-12-04 内蒙古工业大学 Application of active silicon material in preparation of water-retention slow-release microbial fertilizer
CN112662601A (en) * 2021-01-28 2021-04-16 山东九一生物科技股份有限公司 Screening method of microorganisms for repairing petroleum-polluted soil
CN113184873A (en) * 2021-04-23 2021-07-30 内蒙古超牌新材料股份有限公司 Preparation method of molecular sieve, low-nitrogen-adsorption hollow glass drying agent and preparation method thereof
CN113307654A (en) * 2021-06-21 2021-08-27 中科院过程工程研究所南京绿色制造产业创新研究院 Solid waste based porous ceramic composite material and preparation method and application thereof
CN113582194A (en) * 2021-08-24 2021-11-02 广西民族大学 Method for preparing novel zeolite microspheres based on fly ash and novel zeolite microspheres
CN113816687A (en) * 2021-10-15 2021-12-21 王福州 Redundant light heat-preservation waterproof concrete and preparation method thereof
CN113896578A (en) * 2021-10-26 2022-01-07 陕西易达力生物科技有限公司 Organic fertilizer prepared from coal gangue and preparation method thereof
CN114478127A (en) * 2022-03-01 2022-05-13 广西壮族自治区农业科学院 Humic acid fertilizer for relieving continuous cropping obstacle of allium vegetables
CN114605191A (en) * 2022-03-14 2022-06-10 内蒙古蒙苒生物科技有限公司 Modified coal gangue bio-organic fertilizer and preparation method and application thereof
CN114685145A (en) * 2022-04-08 2022-07-01 重庆交通职业学院 Resource treatment method for coal gangue
CN114875016A (en) * 2022-04-29 2022-08-09 重庆西农植物保护科技开发有限公司 Preparation carrier suitable for pseudomonas fluorescens and microbial inoculum thereof
CN115448801A (en) * 2022-09-22 2022-12-09 舒新前 Coal-based solid waste humic acid mineral fertilizer and preparation method and application thereof
CN115536465A (en) * 2022-10-08 2022-12-30 广东石油化工学院 Bio-fertilizer for litchi planting and preparation method thereof
CN116003013A (en) * 2023-02-07 2023-04-25 中国矿业大学 Heat conduction modifier, gangue-based underground heat conduction material and preparation method thereof
CN116114567A (en) * 2022-12-30 2023-05-16 中国科学院武汉岩土力学研究所 Ecological restoration matrix for multi-element solid waste-based mine landfill site and preparation method thereof
CN116114568A (en) * 2022-12-30 2023-05-16 中国科学院武汉岩土力学研究所 Activated gangue-based compressed ecological soil and preparation method thereof
CN117417061A (en) * 2023-12-19 2024-01-19 临沂市环境保护科学研究所有限公司 Composite treating agent for high-concentration ammonia nitrogen sewage and preparation method thereof
CN116003013B (en) * 2023-02-07 2024-06-25 中国矿业大学 Heat conduction modifier, gangue-based underground heat conduction material and preparation method thereof

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CN112028709B (en) * 2020-08-06 2023-04-14 内蒙古工业大学 Application of active silicon material in preparation of water-retention slow-release microbial fertilizer
CN112028709A (en) * 2020-08-06 2020-12-04 内蒙古工业大学 Application of active silicon material in preparation of water-retention slow-release microbial fertilizer
CN112662601A (en) * 2021-01-28 2021-04-16 山东九一生物科技股份有限公司 Screening method of microorganisms for repairing petroleum-polluted soil
CN113184873A (en) * 2021-04-23 2021-07-30 内蒙古超牌新材料股份有限公司 Preparation method of molecular sieve, low-nitrogen-adsorption hollow glass drying agent and preparation method thereof
CN113184873B (en) * 2021-04-23 2022-12-02 内蒙古超牌新材料股份有限公司 Preparation method of molecular sieve, low-nitrogen-adsorption hollow glass drying agent and preparation method thereof
CN113307654A (en) * 2021-06-21 2021-08-27 中科院过程工程研究所南京绿色制造产业创新研究院 Solid waste based porous ceramic composite material and preparation method and application thereof
CN113582194A (en) * 2021-08-24 2021-11-02 广西民族大学 Method for preparing novel zeolite microspheres based on fly ash and novel zeolite microspheres
CN113582194B (en) * 2021-08-24 2022-11-08 广西民族大学 Method for preparing zeolite microspheres based on fly ash and zeolite microspheres
CN113816687A (en) * 2021-10-15 2021-12-21 王福州 Redundant light heat-preservation waterproof concrete and preparation method thereof
CN113896578A (en) * 2021-10-26 2022-01-07 陕西易达力生物科技有限公司 Organic fertilizer prepared from coal gangue and preparation method thereof
CN114478127A (en) * 2022-03-01 2022-05-13 广西壮族自治区农业科学院 Humic acid fertilizer for relieving continuous cropping obstacle of allium vegetables
CN114478127B (en) * 2022-03-01 2022-09-23 广西壮族自治区农业科学院 Humic acid fertilizer for relieving continuous cropping obstacle of allium vegetables
CN114605191A (en) * 2022-03-14 2022-06-10 内蒙古蒙苒生物科技有限公司 Modified coal gangue bio-organic fertilizer and preparation method and application thereof
CN114685145B (en) * 2022-04-08 2022-10-11 重庆交通职业学院 Resource treatment method for coal gangue
CN114685145A (en) * 2022-04-08 2022-07-01 重庆交通职业学院 Resource treatment method for coal gangue
CN114875016A (en) * 2022-04-29 2022-08-09 重庆西农植物保护科技开发有限公司 Preparation carrier suitable for pseudomonas fluorescens and microbial inoculum thereof
CN114875016B (en) * 2022-04-29 2023-10-13 重庆西农植物保护科技开发有限公司 Formulated carrier suitable for pseudomonas fluorescens and microbial inoculum thereof
CN115448801A (en) * 2022-09-22 2022-12-09 舒新前 Coal-based solid waste humic acid mineral fertilizer and preparation method and application thereof
CN115536465A (en) * 2022-10-08 2022-12-30 广东石油化工学院 Bio-fertilizer for litchi planting and preparation method thereof
CN116114567A (en) * 2022-12-30 2023-05-16 中国科学院武汉岩土力学研究所 Ecological restoration matrix for multi-element solid waste-based mine landfill site and preparation method thereof
CN116114568A (en) * 2022-12-30 2023-05-16 中国科学院武汉岩土力学研究所 Activated gangue-based compressed ecological soil and preparation method thereof
CN116114568B (en) * 2022-12-30 2024-04-19 中国科学院武汉岩土力学研究所 Activated gangue-based compressed ecological soil and preparation method thereof
CN116003013A (en) * 2023-02-07 2023-04-25 中国矿业大学 Heat conduction modifier, gangue-based underground heat conduction material and preparation method thereof
CN116003013B (en) * 2023-02-07 2024-06-25 中国矿业大学 Heat conduction modifier, gangue-based underground heat conduction material and preparation method thereof
CN117417061A (en) * 2023-12-19 2024-01-19 临沂市环境保护科学研究所有限公司 Composite treating agent for high-concentration ammonia nitrogen sewage and preparation method thereof
CN117417061B (en) * 2023-12-19 2024-03-01 临沂市环境保护科学研究所有限公司 Composite treating agent for high-concentration ammonia nitrogen sewage and preparation method thereof

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