CN115611683A - Method for preparing water-soluble fertilizer containing super-mineral humic acid by using agriculture and forestry biomass solid waste - Google Patents
Method for preparing water-soluble fertilizer containing super-mineral humic acid by using agriculture and forestry biomass solid waste Download PDFInfo
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- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
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- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
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- C—CHEMISTRY; METALLURGY
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- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
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Abstract
The invention discloses a method for preparing a super-mineral humic acid-containing water-soluble fertilizer by utilizing agriculture and forestry biomass solid wastes. The method takes agriculture and forestry biomass solid wastes as a starting point, carries out gradient roasting carbonization on the wastes under the combined action of a catalyst and an activating agent to promote the recombination of organic carbon chains to obtain a weatherlike coal precursor, enriches functional groups of the weatherlike coal precursor under the action of an oxidizing agent, and converts organic matters into super-mineral humic acid. According to actual requirements, the types and the dosages of the activating agent and the extracting agent are changed, the content of the macroelements in the product is increased, and the super-mineral humic acid-containing water-soluble fertilizer product meeting the technical indexes of macroelement type liquid products in the humic acid-containing water-soluble fertilizer standard is obtained. The invention achieves harmless and resource utilization of agriculture and forestry organic solid wastes through a simple process, reduces the generation of carbon dioxide isothermal chamber gas, obtains a super-mineral source humic acid-containing water-soluble fertilizer product with higher added value, has good economic value and environmental benefit, and is a true carbon-negative technology.
Description
Technical Field
The invention belongs to the technical field of agriculture and forestry solid waste recycling, and particularly relates to a method for preparing a super-mineral humic acid-containing water-soluble fertilizer by using agriculture and forestry biomass solid waste.
Background
The comprehensive utilization of agriculture and forestry biomass solid wastes abroad has been in the history of nearly one hundred years, and the comprehensive utilization means and the comprehensive utilization mode are relatively mature. Especially in developed countries, advanced equipment, perfect policy and system, mature technical process and the like ensure the full utilization of agriculture and forestry biomass solid wastes. Scientific researches of numerous scholars such as Fabrizio Adani (Italy), yasair S.S.Al-Faiyz (Satada), jader Galba Busato (Brazil), paola A.Campitellii (Argentina) and Redouane Mghaiouini (Morocco) show that after the agricultural and forestry biomass solid wastes are composted for 120-240 days under the conditions of proper moisture, atmosphere, acid-base property, carbon-nitrogen ratio and the like, degradable organic matters can be converted into humus, nutrient substances in soil are enriched, the formation of a soil solid grain structure is facilitated, the capacities of water retention, heat preservation, air permeability and fertilizer retention are increased, the scientificity of a composting method is proved, and the sustainable development of foreign agriculture can be guaranteed. Meanwhile, the straws are rich in cellulose, hemicellulose and lignin and are a good feed source for herbivorous livestock. The remaining solid waste utilization of biomass is different in various countries, such as energy farms in the united states, solar plans in japan, alcohol energy plans in brazil, straw power generation technology in denmark, and the like.
The agricultural and forestry biomass solid waste has high organic matter content and is a precious natural renewable resource; but the biomass solid waste returning rate is low, and the problems of land hardening, plant diseases and insect pests and the like are easily caused. And because the feed, biogas and humic acid technology is immature and the utilization rate is low, a large amount of biomass solid waste is combusted and utilized, the value of the biomass solid waste is far from being completely developed, and great resource waste is caused. At present, the carbon emission of different recycling modes of agriculture and forestry biomass solid waste is sequenced from large to small in sequence as follows: incineration energy regeneration, biochemical fertilizer treatment, feed treatment, methane energy regeneration and humic acidification. Therefore, development of low-carbon and environment-friendly process technology is urgently needed.
Humic acid is widely applied to various fields of agriculture, forestry, pasture, petroleum, chemical industry, building materials, medicine, sanitation, environmental protection and the like. The method maintains the atmospheric carbon cycle in large environment, large agriculture, large industry and large medical insurance, reduces the emission of greenhouse gases, and has the special low-carbon characteristic of exerting the function of green leaves. In the aspect of agriculture, the humic acid fertilizer has the functions of obvious fertilizer synergism, soil improvement, crop growth stimulation, agricultural product quality improvement and the like. Humic acid fertilizer is highly advocated in modern agricultural production advocating ecological agricultural construction, pollution-free agricultural production, green food and pollution-free environment-friendly fertilizer. Traditionally, humic acid is produced by mainly taking weathered coal, lignite and peat as raw materials and adopting an alkali extraction method to extract a humic acid product. However, the coal resources in China are mainly distributed in northwest areas such as inner Mongolia, xinjiang, shaanxi and Shanxi and southwest areas such as Guangxi and Yunnan, are affected by regions and need to be transported for a long distance, so that the production cost of enterprises is high. Meanwhile, coal is a solid combustible mineral formed gradually by burying ancient plants underground and undergoing complex biochemical and physicochemical changes, is an unrecoverable resource, is consumed greatly, has an increased price, and needs to be replaced by other renewable resources.
Although the research on humic acid starts late in China, research works such as a composting method, a fermentation method, a hydrothermal method and the like have a great deal of research in China, and the research and application of the methods are all at international leading level, for example, CN102936159A discloses a method for preparing compost by using beer production waste, and vinasse and sludge produced in beer production are used as raw materials to be stacked for 13-17 days to obtain humus fertilizer; 5363 and adding exogenous substances to compost, such as Yang Xiaoying, so as to accelerate the composting process and improve the composting quality; CN113501644A discloses a preparation for improving organic solid waste fermentation efficiency, a preparation method and application thereof, wherein the preparation comprises immobilized biological enzyme, co-metabolic nutrient substances and organic polymer; zhao Jianliang and the like, waste seaweed residues discharged from seaweed production are used as raw materials, and biological humic acid is obtained through microbial fermentation; patent CN114292145A discloses a preparation method of an artificial humic acid urea slow release fertilizer, biomass is converted into fulvic acid and humic acid by a hydrothermal method, and the fulvic acid urea slow release fertilizer is obtained by mixing the fulvic acid and humic acid with a urea solution. On the basis of the methods, a plurality of new preparation methods are further developed in China, for example, a hydrolysis method developed by Huang Chen is adopted, cellulose, hemicellulose, lignin and the like are hydrolyzed by dilute acid, and then bacteria are added, concentrated and fermented for 3-5 days to obtain a liquid humic acid fertilizer; wang Xiufei and the like, a chemical oxidation degradation method is developed, a new functional group is introduced after oxidation degradation, and then chemical modification treatment is carried out to obtain humic acid; CN113399417A discloses a method for preparing sodium humate by using sludge and application thereof, wherein low-temperature roasting oxidation is adopted, biomass is roasted and carbonized under alkaline conditions, and then activated and oxidized to obtain a humate product; CN113277492A discloses a method for preparing potassium humate and biochar from agricultural and forestry waste, which comprises the steps of roasting the agricultural and forestry waste and potassium ferrate in vacuum and then quenching the roasted agricultural and forestry waste with water to obtain the potassium humate and the biochar. The methods improve the yield of the humic acid product, and are rapid and efficient. However, the composting method is long in time, needs land rotation tillage and is not suitable for the basic national conditions of China. The fermentation method is difficult to simulate the soil environment for cultivating specific strains, the strain screening and enriching technology is not mature, the problems of low yield, unstable product quality and the like often occur in an amplification experiment, and the large-scale application is difficult to realize. The hydrothermal method has high requirements on reaction equipment conditions and high energy consumption during engineering amplification, is not suitable for large-scale industrial production, and the fundamental problems are difficult to solve. The hydrolysis method and the chemical oxidation degradation method also cannot fundamentally overcome the limitations of the fermentation method and the hydrothermal method, only the low-temperature roasting oxidation method is fundamentally changed, the process is simple, the energy consumption is low, and if the low-temperature roasting oxidation method is applied to the preparation of the humic acid organic fertilizer by the biomass, the industrial production is expected to be realized.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a method for preparing a super-mineral humic acid-containing water-soluble fertilizer by utilizing agriculture and forestry biomass solid wastes.
Cleaning and mechanically grinding the agricultural and forestry biomass solid wastes such as cotton stalks, rice husks, trees and the like, mixing the agricultural and forestry biomass solid wastes with a catalyst and an activating agent according to a certain proportion, and carrying out gradient roasting carbonization, wherein the catalyst can reduce the activation energy of decomposition and polymerization reactions of lignin, cellulose, hemicellulose and the like in the carbonization process, accelerate carbon chain recombination to obtain a weatherlike coal product, and the activating agent can be used for preferentially carbonizing the lignin, the cellulose, the hemicellulose and the like, reduce the occurrence of thermal decomposition phenomenon and provide nutrient elements; mixing the weatherlike coal product obtained by carbonization with an oxidant according to a certain proportion, performing targeted oxidation on functional groups, promoting the functional groups to stretch and deform in the oxidation process, and simultaneously adding hydroxyl and phenolic groups to convert the weatherlike coal product into super-mineral humic acid; finally, an extracting agent is added to extract the super-mineral humic acid to obtain a primary product, a liquid product containing the super-mineral humic acid water-soluble fertilizer (macroelement type) can be obtained after concentration or dilution, and further, a concentration granulation process combining triple effect evaporation and a spray drying process can be adopted to prepare the product into a granular super-mineral humic acid water-soluble fertilizer (macroelement type) solid product, so that the product is convenient to transport, and the economic benefit maximization is realized. Finally, the harmless and resource utilization of the organic solid wastes of agriculture and forestry is achieved through a simple and convenient process, the super-mineral humic acid-containing water-soluble fertilizer (macroelement type) product with higher added value is obtained while the generation of carbon dioxide isothermal gas is reduced, and the method has good economic value and environmental benefit and is a true 'carbon negative' technology.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a super-mineral humic acid-containing water-soluble fertilizer by utilizing agriculture and forestry biomass solid wastes comprises the following steps:
(1) Heating ferric salt at 100-300 deg.c for 6-18 hr to obtain hydroxyl ferric oxide and/or ferric oxide catalyst;
(2) Uniformly mixing the catalyst obtained in the step (1), biomass solid waste powder and an activating agent, roasting at the temperature of between room temperature and 150 ℃ for 1 to 2 hours in an air atmosphere, roasting at the temperature of between 150 and 200 ℃ for 1 to 2 hours with the volume content of oxygen of between 10 and 15 percent, and roasting at the temperature of between 200 and 300 ℃ for 1 to 2 hours with the volume content of oxygen of between 0 and 10 percent to obtain a weatherlike coal precursor;
(3) Mixing the weatherlike coal precursor obtained in the step (2) with an oxidant aqueous solution, activating for 24-72 h at 60-100 ℃, adding the obtained oxidation product into an extractant solution, extracting for 3-6 h, and performing solid-liquid separation;
(4) Magnetically separating the solid residue obtained in the step (3) to recover the catalyst, and taking the rest as a base fertilizer raw material containing the humic acid compound fertilizer;
(5) And (4) concentrating and granulating the liquid obtained in the step (3) to obtain a liquid product containing the super-mineral humic acid water-soluble fertilizer (macroelement type), namely a solid product containing the super-mineral humic acid water-soluble fertilizer (macroelement type).
Preferably, the iron salt in step (1) is at least one of ferric chloride, ferric nitrate, ferric acetate and ferric sulfate.
Preferably, the ferric salt in the step (1) is subjected to hydrothermal reaction at 100-200 ℃ to obtain iron oxyhydroxide; carrying out hydrothermal reaction at 200-300 ℃ to obtain the ferric oxide.
Preferably, the average particle size of the iron oxyhydroxide and/or iron oxide catalyst in the step (1) is less than or equal to 500nm.
Preferably, the particle size of the biomass solid waste powder in the step (2) is less than or equal to 0.150mm, and the biomass solid waste powder is obtained by cleaning and then mechanically grinding the agricultural and forestry biomass solid waste.
Preferably, the biomass solid waste powder raw material in the step (2) is at least one of cotton stalks, rice hulls and trees.
Preferably, the dosage of the catalyst in the step (2) is 0.05-1% of the mass of the biomass solid waste powder; more preferably 0.2 to 0.5%.
Preferably, the activating agent of step (2) is K 3 PO 4 、K 2 HPO 4 、KH 2 PO 4 、KNO 3 、KNO 2 And K 2 CO 3 At least one of (1).
Preferably, the dosage of the activating agent in the step (2) is 10-50% of the mass of the biomass solid waste powder; more preferably 25 to 30%.
Preferably, in the aqueous solution of the oxidizing agent in the step (3), the oxidizing agent is KMnO 4 、H 2 O 2 、HNO 3 、CH 3 COOOH and (NH) 4 ) 2 S 2 O 8 At least one of; the using amount of the oxidant is 1-10% of the mass of the biomass solid waste powder in the step (2); more preferably 4%.
Preferably, the mass fraction of the oxidant aqueous solution in the step (3) is 0.5-5%; more preferably 1%.
Preferably, step (3)) In the extractant solution, the extractant is KOH or K 2 CO 3 、K 4 P 2 O 7 And K 2 C 2 O 4 At least one of; the dosage of the extractant is 2-20% of the mass of the biomass solid waste powder in the step (2); more preferably 6%.
Preferably, the mass fraction of the extractant solution in the step (3) is 1-10%; more preferably 3%.
Preferably, the liquid product containing the super-mineral humic acid water-soluble fertilizer (macroelement type) in the step (5) is concentrated or diluted to be used as the water-soluble fertilizer (macroelement type).
Preferably, the concentration and granulation in the step (5) adopts a concentration and granulation process combining triple effect evaporation and a spray drying process.
The principle of the method is as follows:
the method comprises the steps of cleaning and mechanically grinding the agricultural and forestry biomass solid wastes such as cotton stalks, rice hulls and trees, mixing the agricultural and forestry biomass solid wastes with a catalyst and an activating agent according to a certain proportion, and performing gradient roasting and carbonization, wherein the catalyst is ferric oxide and hydroxyl ferric oxide with the particle size of less than 500nm, and has the main function of promoting the breaking and recombination of carbon chains of substances such as cellulose, hemicellulose and lignin in the biomass solid wastes at a certain temperature; the activating agent has the function of fixing organic functional groups in the agriculture and forestry biomass solid waste to reduce the occurrence of thermal decomposition, and can be used as a source of elements such as K, N, P to improve the content of macroelements in carbonized products. The carbonized product is mixed with an oxidant according to a certain proportion and is subjected to functional group targeted oxidation, and the oxidant mainly has the functions of promoting the functional group to stretch and deform and simultaneously increasing hydroxyl and phenolic groups so that the coal-like product obtained by carbonization is converted into the humic acid with super mineral sources. And finally, adding an extracting agent to extract the super-mineral humic acid to obtain a primary product, and further supplementing K, P macroelements to the product while extracting the super-mineral humic acid so as to meet the requirement of macroelement content in the technical index of macroelement water-soluble fertilizer products. And the catalyst in the extracted residues is recycled by magnetic separation, and the rest is used as a base fertilizer raw material of the humic acid-containing compound fertilizer, so that the full utilization of biomass solid waste is realized. The extract can be concentrated or diluted to obtain a liquid product of the super-mineral humic acid-containing water-soluble fertilizer (macroelement type), and further, the product can be granulated by adopting a concentration granulation process combining triple effect evaporation and spray drying processes to obtain a solid product of the super-mineral humic acid-containing water-soluble fertilizer (macroelement type), so that the product is convenient to transport, and the economic benefit is maximized.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention adopts a method of carbonization-oxidation-extraction step by step, so that the conversion rate of organic matters in the agriculture and forestry biomass solid waste is greatly improved to 50-90%;
(2) The catalyst and the oxidant used in the invention can recombine and target-oxidize organic carbon chains in the agricultural and forestry biomass solid wastes, increase the content of macromolecular humic acid and simultaneously reduce the content of fulvic acid, and the catalyst can be recycled, and the part which cannot be recycled (less than or equal to 30 percent) and solid waste residues are used as the base fertilizer raw material of the humic acid-containing compound fertilizer to provide a certain amount of trace elements;
(3) The activating agent and the extracting agent used in the invention contain nitrogen, phosphorus and potassium elements which are converted into major elements in the target product, thereby improving the agricultural value and the economic benefit of the super-mineral humate product;
(4) In the carbonization and oxidation stages, organic matter functional groups are modified, hydroxyl groups and phenol groups are added, the water solubility and the aromaticity are improved, and a super-mineral humic acid product is obtained;
(5) The method has the advantages of simple process, mild reaction conditions, low energy consumption and large treatment capacity, can realize large-scale continuous industrial production, and realizes 'changing waste into valuable'.
Drawings
FIG. 1 is a transmission electron micrograph of the nano iron oxide catalyst of example 1;
FIG. 2 is a transmission electron micrograph of an iron oxyhydroxide catalyst according to example 1;
FIG. 3 is a transmission electron micrograph of iron oxide obtained after decomposition of potassium ferrate in comparative example 3;
FIG. 4 is a Fourier transform infrared absorption spectrometer of a solid product containing a super-mineral humic acid water-soluble fertilizer (macroelement type) obtained in example 1;
FIG. 5 is a flow chart of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1) Weighing 100g of agriculture and forestry biomass (a mixture of cotton stalks and cedar sawdust in a mass ratio of 2:1) solid waste powder which is mechanically ground and sieved by a 100-mesh sieve;
(2) Carrying out hydrothermal treatment on ferric chloride at 150 ℃ for 12h to obtain iron oxyhydroxide, and carrying out hydrothermal treatment on ferric nitrate at 220 ℃ for 12h to obtain ferric oxide;
(3) 100g of biomass powder was mixed with a catalyst (100 mg of iron oxide, 100mg of iron oxyhydroxide) and an activator (10 g K) 2 HPO 4 、10g KNO 3 、5g K 2 CO 3 ) Mixing, regulating and controlling the oxygen content of atmosphere and carrying out temperature programming, reacting for 2h under the atmosphere of 100 ℃, reacting for 2h with the oxygen volume content of 10% at 200 ℃, and reacting for 2h with the oxygen volume content of 5% at 300 ℃ to obtain a weatherlike coal precursor;
(4) The weatherlike coal product obtained in the step (3) and an oxidant solution (300 mL of H with the mass fraction of 1% 2 O 2 Solution, 100mL of CH with a mass fraction of 1% 3 COOOH solution), and stirring at 80 ℃ for 24 hours for activation to obtain an oxidation product;
(5) Mixing the oxidation product obtained in the step (4) with an extractant solution (300 mL of KOH solution with the mass fraction of 1% and 200mL of K with the mass fraction of 1% 2 CO 3 Solution, 100mL of 1% by mass K 4 P 2 O 7 Solution), mixing and stirring, and centrifuging after 6 hours;
(6) Centrifugally separating solid residues in the step (5) to obtain a mixture of the catalyst and the carbonized residues, performing magnetic separation, respectively drying, wherein the mass of the recovered catalyst is 0.19g, and the balance of 10.7g is used as a base fertilizer raw material containing the humic acid compound fertilizer;
(7) The liquid obtained by centrifugal separation in the step (5) is a primary product of the water-soluble fertilizer containing the humic acid with the super mineral source, and the primary product is concentrated or diluted to obtain a liquid product of the water-soluble fertilizer (macroelement type) containing the humic acid with the super mineral source; and then concentrating and granulating to obtain 109g of solid product containing the super-mineral humic acid water-soluble fertilizer (macroelement type).
In the embodiment, 100g of biomass solid waste is treated, the addition amount of the catalyst is 0.20g, the amount of the activating agent is 25g, the amount of the oxidizing agent is about 4g, and the amount of the extracting agent is about 6g, after the reaction is finished, the concentrated granulation is carried out to obtain 109g of solid product containing the super-mineral humic acid water-soluble fertilizer (macroelement type), 0.19g of the catalyst is separated and recovered by magnetic separation, and the total amount of the unrecovered catalyst and the unreacted biomass residue is 10.7g.
Comparative example 1
(1) Weighing 10kg of agriculture and forestry biomass (mixture of cotton stalks and cedar sawdust in a mass ratio of 2:1) solid waste powder which is mechanically ground and sieved by a 100-mesh sieve;
(2) 10kg of biomass powder and an activator (1 kg of K) 2 CO 3 、1kg K 2 HPO 4 、1kg KH 2 PO 4 ) Mixing, regulating and controlling the oxygen content of atmosphere, carrying out temperature programming, carrying out reaction for 2h at 100 ℃ in the air atmosphere, carrying out reaction for 1h at 150 ℃ with the volume content of oxygen of 10 percent, and carrying out reaction for 1h at 300 ℃ under an anaerobic condition to obtain a weatherlike coal precursor;
(3) The weatherlike coal product obtained in the step (2) and an oxidant solution (20L of H with the mass fraction of 1% 2 O 2 1L of HNO with the mass fraction of 1% 3 20L of 1% by mass CH 3 COOOH solution), and stirring for 24 hours at 80 ℃ for activation;
(4) The oxidation product obtained in the step (3) and an extraction agent solution (40L of KOH solution with the mass fraction of 1 percent, 10L of K with the mass fraction of 1 percent) 2 CO 3 Solution, 10L of 1% by mass K 2 C 2 O 4 Solution), mixing and stirring, and centrifuging after 6 hours;
(5) Centrifugally separating solid residues in the step (4), drying to 4193g, and using the solid residues as a base fertilizer raw material containing the humic acid compound fertilizer;
(6) The liquid obtained by centrifugal separation in the step (4) is a primary product of the water-soluble fertilizer containing the humic acid with the super mineral source, and the primary product is concentrated or diluted to obtain a liquid product of the water-soluble fertilizer (macroelement type) containing the humic acid with the super mineral source; and then concentrated and granulated to obtain 6.1kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type).
In this example, 10kg of biomass solid waste, 3kg of activating agent, about 410g of oxidizing agent and about 600g of extracting agent are treated, and after the reaction is finished, 6.1kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type) is obtained by concentration and granulation, and the total amount of solid residue is 4193g.
Example 2
(1) Weighing 10kg of agriculture and forestry biomass (mixture of cotton stalks and cedar sawdust in a mass ratio of 2:1) solid waste powder which is mechanically ground and sieved by a 100-mesh sieve;
(2) Carrying out hydrothermal treatment on ferric nitrate at 220 ℃ for 12 hours to obtain ferric oxide;
(3) 10kg of biomass powder was mixed with a catalyst (20 g of iron oxide) and an activator (1 kg of K) 2 CO 3 、1kg K 2 HPO 4 、1kg KH 2 PO 4 ) Mixing, regulating and controlling the oxygen content of atmosphere, carrying out temperature programming, carrying out reaction for 2h at 100 ℃ in the air atmosphere, carrying out reaction for 1h at 150 ℃ with the volume content of oxygen of 10 percent, and carrying out reaction for 1h at 300 ℃ under an anaerobic condition to obtain a weatherlike coal precursor;
(4) The weatherlike coal product obtained in the step (3) and an oxidant solution (20L of H with the mass fraction of 1% 2 O 2 1L of HNO with the mass fraction of 1% 3 20L of 1% by mass CH 3 COOOH solution), and stirring for 24 hours at 80 ℃ for activation;
(5) Oxidizing product obtained in the step (4) and an extracting agent solution (40L of KOH solution with the mass fraction of 1 percent and 10L of K with the mass fraction of 1 percent) 2 CO 3 Solution, 10L of 1% by mass K 2 C 2 O 4 Solution), mixing and stirring, and centrifuging after 6 hours;
(6) Centrifugally separating solid residues in the step (5) to obtain a mixture of the catalyst and carbonized residues, performing magnetic separation, respectively drying, wherein the mass of the recovered catalyst is 17.6g, and the balance of 2433g is used as a base fertilizer raw material containing the humic acid compound fertilizer;
(7) The liquid obtained by centrifugal separation in the step (5) is a primary product of the water-soluble fertilizer containing the humic acid with the super mineral source, and the primary product is concentrated or diluted to obtain a liquid product of the water-soluble fertilizer (macroelement type) containing the humic acid with the super mineral source; and then concentrated and granulated to obtain 9.4kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type).
In the embodiment, 10kg of biomass solid waste is treated, the addition amount of the catalyst is 20g, the addition amount of the activator is 3kg, the addition amount of the oxidant is about 410g, and the extraction agent is about 600g, after the reaction is finished, the concentrated granulation is carried out to obtain 9.4kg of super-mineral humic acid-containing water-soluble fertilizer (macroelement type) solid product, 17.6g of the catalyst is separated and recovered by magnetic separation, and the total amount of the unrecovered catalyst and unreacted biomass residue is 2433g. Compared with the comparative example 1, the iron oxide has good catalytic action, promotes the conversion of the biomass to humic acid, and reduces the decomposition and carbonization of the biomass.
Example 3
(1) Weighing 10kg of agriculture and forestry biomass (mixture of cotton stalks and cedar sawdust in a mass ratio of 2:1) solid waste powder which is mechanically ground and sieved by a 100-mesh sieve;
(2) Carrying out hydrothermal treatment on ferric chloride at 150 ℃ for 12h to obtain iron oxyhydroxide;
(3) 10kg of biomass powder was mixed with a catalyst (20 g of iron oxyhydroxide) and an activator (1 kg of K) 2 CO 3 、1kg K 2 HPO 4 、1kg KH 2 PO 4 ) Mixing, regulating and controlling the oxygen content of atmosphere, carrying out temperature programming, carrying out reaction for 2h at 100 ℃ in the air atmosphere, carrying out reaction for 1h at 150 ℃ with the volume content of oxygen of 10 percent, and carrying out reaction for 1h at 300 ℃ under an anaerobic condition to obtain a weatherlike coal precursor;
(4) The weatherlike coal product obtained in the step (3) and an oxidant solution (20L of H with the mass fraction of 1% 2 O 2 1L of HNO with the mass fraction of 1% 3 20L of 1% by mass CH 3 COOOH solution), and stirring for 24 hours at 80 ℃ for activation;
(5) Oxidizing product obtained in the step (4) and an extracting agent solution (40L of KOH solution with the mass fraction of 1 percent and 10L of K with the mass fraction of 1 percent) 2 CO 3 Solution, 10L of 1% by mass K 2 C 2 O 4 Solution), mixing and stirring, and centrifuging after 6 hours;
(6) Centrifugally separating solid residues in the step (5) to obtain a mixture of the catalyst and the carbonized residues, performing magnetic separation, respectively drying, wherein the mass of the recovered catalyst is 17.5g, and 2319g of the rest is used as a base fertilizer raw material containing the humic acid compound fertilizer;
(7) The liquid obtained by centrifugal separation in the step (5) is a primary product of the water-soluble fertilizer containing the humic acid with the super mineral source, and the primary product is concentrated or diluted to obtain a liquid product of the water-soluble fertilizer (macroelement type) containing the humic acid with the super mineral source; and then concentrated and granulated to obtain 9.5kg of solid super-mineral humic acid-containing water-soluble fertilizer (macroelement type) solid product.
In the embodiment, 10kg of biomass solid waste is treated, the adding amount of the catalyst is 20g, the activating agent is 3kg, the oxidizing agent is about 410g, and the extracting agent is about 600g, after the reaction is finished, the mixture is concentrated and granulated to obtain 9.5kg of a super-mineral humic acid-containing water-soluble fertilizer (macroelement type) solid product, 17.5g of the catalyst is separated and recovered through magnetic separation, and 2319g of the catalyst and unreacted biomass residue which are not recovered are combined. Compared with the comparative example 1, the iron oxyhydroxide has good catalytic action, promotes the conversion of the biomass to humic acid, and reduces the decomposition and carbonization of the biomass.
Example 4
(1) Weighing 10kg of agriculture and forestry biomass (a mixture of cotton stalks and cedar sawdust in a mass ratio of 2:1) solid waste powder which is mechanically ground and sieved by a 100-mesh sieve;
(2) Carrying out hydrothermal treatment on ferric chloride at 150 ℃ for 12h to obtain iron oxyhydroxide, and carrying out hydrothermal treatment on ferric nitrate at 220 ℃ for 12h to obtain ferric oxide;
(3) 10kg of biomass powder was mixed with a catalyst (10 g of iron oxide, 10g of iron oxyhydroxide) and an activator (1 kg of K) 2 CO 3 、1kg K 2 HPO 4 、1kg KH 2 PO 4 ) Mixing, regulating and controlling the oxygen content of atmosphere, carrying out temperature programming, carrying out reaction for 2h at 100 ℃ in the air atmosphere, carrying out reaction for 1h at 150 ℃ with the volume content of oxygen of 10 percent, and carrying out reaction for 1h at 300 ℃ under an anaerobic condition to obtain a weatherlike coal precursor;
(4) The weatherlike coal product obtained in the step (3) and an oxidant solution (20L of H with the mass fraction of 1% 2 O 2 1L of HNO with the mass fraction of 1% 3 20L of 1% CH 3 COOOH solution), and stirring for 24 hours at 80 ℃ for activation;
(5) Oxidizing product obtained in the step (4) and an extracting agent solution (40L of KOH solution with the mass fraction of 1 percent and 10L of K with the mass fraction of 1 percent) 2 CO 3 Solution, 10L of 1% by mass K 2 C 2 O 4 Solution), mixing and stirring, and centrifuging after 6 hours;
(6) Centrifugally separating solid residues in the step (5) to obtain a mixture of the catalyst and carbonized residues, performing magnetic separation, respectively drying, wherein the mass of the recovered catalyst is 17.6g, and the balance of 1552g is used as a base fertilizer raw material containing the humic acid compound fertilizer;
(7) The liquid obtained by centrifugal separation in the step (5) is a primary product of the water-soluble fertilizer containing the humic acid with the super mineral source, and the primary product is concentrated or diluted to obtain a liquid product of the water-soluble fertilizer (macroelement type) containing the humic acid with the super mineral source; then 10.5kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type) is obtained by concentration and granulation.
In the embodiment, 10kg of biomass solid waste is treated, the addition amount of the catalyst is 20g, the addition amount of the activator is 3kg, the addition amount of the oxidant is about 410g, and the extraction agent is about 600g, after the reaction is finished, the concentrated granulation is carried out to obtain 10.5kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type), 17.6g of catalyst is recovered by magnetic separation, and 1552g of catalyst which is not recovered and unreacted biomass residue are combined. In comparison with examples 2 and 3, it was confirmed that in examples 2 and 3, only one catalyst was used, and each catalyst was effective, but it was apparently more effective when mixed in a certain ratio.
Comparative example 2
(1) Weighing 10kg of agriculture and forestry biomass (mixture of cotton stalks and cedar sawdust in a mass ratio of 2:1) solid waste powder which is mechanically ground and sieved by a 100-mesh sieve;
(2) 10kg of biomass powder was mixed with a catalyst (20 g of potassium ferrate) and an activator (1 kg of K) 2 CO 3 、1kg K 2 HPO 4 、1kg KH 2 PO 4 ) Mixing, regulating and controlling the oxygen content of atmosphere, carrying out temperature programming, carrying out reaction for 2h at 100 ℃ in the air atmosphere, carrying out reaction for 1h at 150 ℃ with the volume content of oxygen of 10 percent, and carrying out reaction for 1h at 300 ℃ under an anaerobic condition to obtain a weatherlike coal precursor;
(3) The weatherlike coal product obtained in the step (2) and an oxidant solution (20L of H with the mass fraction of 1% 2 O 2 1L of HNO with the mass fraction of 1% 3 20L of 1% by mass CH 3 COOOH solution), and stirring for 24 hours at 80 ℃ for activation;
(4) The oxidation product obtained in the step (3) and an extraction agent solution (40L of KOH solution with the mass fraction of 1 percent, 10L of K with the mass fraction of 1 percent) 2 CO 3 Solution, 10L of 1% by mass K 2 C 2 O 4 Solution), mixing and stirring, and centrifuging after 6 hours;
(5) Centrifugally separating solid residues in the step (4) to obtain a mixture of the catalyst and the carbonized residues, performing magnetic separation, and respectively drying, wherein the mass of the recovered catalyst is only 6.7g due to more residues, and 3855g of the rest residues are used as a base fertilizer raw material containing the humic acid compound fertilizer;
(6) The liquid obtained by centrifugal separation in the step (4) is a primary product of the water-soluble fertilizer containing the humic acid with the super mineral source, and the primary product is concentrated or diluted to obtain a liquid product of the water-soluble fertilizer (macroelement type) containing the humic acid with the super mineral source; and then 6.8kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type) is obtained through concentration and granulation.
In the embodiment, 10kg of biomass solid waste is treated, the addition amount of the catalyst is 20g, the addition amount of the activator is 3kg, the addition amount of the oxidant is about 410g, and the extraction agent is about 600g, after the reaction is finished, the concentrated granulation is carried out to obtain 6.8kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type), the catalyst is separated and recovered by magnetic separation by 6.7g, and the total amount of the unrecovered catalyst and unreacted biomass residue is 3855g. Compared with the comparative example 1 and the example 2, the results of the potassium humate yield measurement confirm that the iron oxide obtained by decomposing potassium ferrate has certain effect as the catalyst, but the potassium humate content in 6.1kg of the product in the comparative example 1 is 4.65kg, the potassium humate content in 6.8kg of the product in the comparative example is 5.16kg, which is only increased by 11%, and the effect is obviously poorer compared with the potassium humate content in 10.5kg of the product obtained by the nano iron oxide catalyst in the example 2, which is 7.16kg, and the yield is increased by 54%.
Comparative example 3
(1) Weighing 10kg of agriculture and forestry biomass (mixture of cotton stalks and cedar sawdust in a mass ratio of 2:1) solid waste powder which is mechanically ground and sieved by a 100-mesh sieve;
(2) Roasting potassium ferrate at 300 ℃ for 2h to obtain decomposed ferric oxide;
(3) 10kg of biomass powder was mixed with a catalyst (20 g of iron oxide obtained by decomposing potassium ferrate)) Activator (1 kg K) 2 CO 3 、1kg K 2 HPO 4 、1kg KH 2 PO 4 ) Mixing, regulating and controlling the oxygen content of atmosphere, carrying out temperature programming, carrying out reaction for 2h at 100 ℃ in the air atmosphere, carrying out reaction for 1h at 150 ℃ with the volume content of oxygen of 10 percent, and carrying out reaction for 1h at 300 ℃ under an anaerobic condition to obtain a weatherlike coal precursor;
(4) The weatherlike coal product obtained in the step (3) and an oxidant solution (20L of H with the mass fraction of 1% 2 O 2 1L of HNO with the mass fraction of 1% 3 20L of 1% by mass CH 3 COOOH solution), and stirring for 24 hours at 80 ℃ for activation;
(5) Oxidizing product obtained in the step (4) and an extracting agent solution (40L of KOH solution with the mass fraction of 1 percent and 10L of K with the mass fraction of 1 percent) 2 CO 3 Solution, 10L of 1% by mass K 2 C 2 O 4 Solution), and after 6 hours, centrifugal separation is carried out;
(6) Centrifugally separating solid residues in the step (5) to obtain a mixture of the catalyst and the carbonized residues, performing magnetic separation, respectively drying, wherein the mass of the recovered catalyst is 6.5g, and 3839g of the rest is used as a base fertilizer raw material containing the humic acid compound fertilizer;
(7) The liquid obtained by centrifugal separation in the step (5) is a primary product of the water-soluble fertilizer containing the humic acid with the super mineral source, and the primary product is concentrated or diluted to obtain a liquid product of the water-soluble fertilizer (macroelement type) containing the humic acid with the super mineral source; and then concentrated and granulated to obtain 6.8kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type).
In the embodiment, 10kg of biomass solid waste is treated, the addition amount of the catalyst is 20g, the addition amount of the activator is 3kg, the addition amount of the oxidant is about 410g, and the extraction agent is about 600g, after the reaction is finished, the concentrated granulation is carried out to obtain 6.8kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type), 6.5g of the catalyst is separated and recovered by magnetic separation, and the total amount of the unrecovered catalyst and unreacted biomass residue is 3839g. In comparison with comparative example 1, the use of the iron oxide obtained by decomposition of potassium ferrate as a catalyst did have a certain effect, and the results substantially match comparative example 2, and indeed the iron oxide obtained by decomposition of potassium ferrate had a certain catalytic effect therein, but the effect of the decomposition of potassium ferrate to obtain iron oxide was significantly inferior to that of the nano-sized iron oxide catalyst used in comparative example 2.
Comparative example 4
(1) Weighing 10kg of agriculture and forestry biomass (mixture of cotton stalks and cedar sawdust in a mass ratio of 2:1) solid waste powder which is mechanically ground and sieved by a 100-mesh sieve;
(2) Carrying out hydrothermal treatment on ferric chloride at 150 ℃ for 12h to obtain iron oxyhydroxide, and carrying out hydrothermal treatment on ferric nitrate at 220 ℃ for 12h to obtain ferric oxide;
(3) 10kg of biomass powder was mixed with a catalyst (10 g of iron oxide, 10g of iron oxyhydroxide) and an activator (1 kg of K) 2 CO 3 、1kg K 2 HPO 4 、1kg KH 2 PO 4 ) Mixing, regulating and controlling the oxygen content of atmosphere, carrying out temperature programming, carrying out reaction for 2h at 100 ℃ in air atmosphere, carrying out reaction for 1h at 150 ℃ in air atmosphere, and carrying out reaction for 1h at 300 ℃ in air atmosphere to obtain a weatherlike coal precursor;
(4) The weatherlike coal product obtained in the step (3) and an oxidant solution (20L of H with the mass fraction of 1% 2 O 2 1L of HNO with the mass fraction of 1% 3 20L of 1% by mass CH 3 COOOH solution), and stirring for 24 hours at 80 ℃ for activation;
(5) Oxidizing product obtained in the step (4) and an extracting agent solution (40L of KOH solution with the mass fraction of 1 percent and 10L of K with the mass fraction of 1 percent) 2 CO 3 Solution, 10L of 1% by mass K 2 C 2 O 4 Solution), mixing and stirring, and centrifuging after 6 hours;
(6) Centrifugally separating solid residues in the step (5) to obtain a mixture of the catalyst and carbonized residues, performing magnetic separation, respectively drying, wherein the mass of the recovered catalyst is 17.7g, and the balance of 3191g is used as a base fertilizer raw material containing the humic acid compound fertilizer;
(7) The liquid obtained by centrifugal separation in the step (5) is a primary product of the water-soluble fertilizer containing the humic acid with the super mineral source, and the primary product is concentrated or diluted to obtain a liquid product of the water-soluble fertilizer (macroelement type) containing the humic acid with the super mineral source; and then concentrated and granulated to obtain 6.8kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type).
In the embodiment, 10kg of biomass solid waste is treated, the addition amount of the catalyst is 20g, the addition amount of the activator is 3kg, the addition amount of the oxidant is about 410g, and the extraction agent is about 600g, after the reaction is finished, the concentrated granulation is carried out to obtain 6.8kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type), 17.7g of catalyst is separated and recovered by magnetic separation, and the total amount of the unrecovered catalyst and unreacted biomass residue is 3191g. Compared with example 4, the atmosphere of step 2 is not controlled in the comparative example, the product is obviously less at the end of step 2, a large amount of oxidative decomposition occurs, and finally the quality of potassium humate and residues shows that not only the oxidative decomposition amount is increased, but also the carbonization is serious.
Example 5
(1) Weighing 100kg of agriculture and forestry biomass (mixture of cotton stalks and cedar sawdust in a mass ratio of 2:1) solid waste powder which is mechanically ground and sieved by a 100-mesh sieve;
(2) Carrying out hydrothermal treatment on ferric chloride at 150 ℃ for 12h to obtain iron oxyhydroxide, and carrying out hydrothermal treatment on ferric nitrate at 220 ℃ for 12h to obtain ferric oxide;
(3) 100kg of biomass powder was mixed with a catalyst (100 g of iron oxide, 100g of iron oxyhydroxide) and an activator (5 kg of KNO) 3 、5kg KNO 2 、5kg K 2 HPO 4 、5kg KH 2 PO 4 、5kg K 2 CO 3 ) Mixing, regulating and controlling the oxygen content of atmosphere and carrying out temperature programming, carrying out reaction in the air atmosphere at 100 ℃ for 2h, carrying out reaction at 200 ℃ for 10% by volume of oxygen for 1h, and carrying out reaction at 300 ℃ for 5% by volume of oxygen for 1h to obtain a weatherlike coal precursor;
(4) The weatherlike coal product obtained in the step (3) and an oxidant solution (300L of H with the mass fraction of 1% 2 O 2 Solution, 10L HNO with mass fraction of 1% 3 90L of CH with a mass fraction of 1% 3 COOOH solution), and stirring for 24 hours at 80 ℃ for activation;
(5) Oxidizing product obtained in the step (4) and an extracting agent solution (200L of KOH solution with the mass fraction of 1 percent and 200L of K with the mass fraction of 1 percent) 2 CO 3 Solution, 100mL of 1% by mass K 4 P 2 O 7 Solution, 100mL of 1% by mass K 2 C 2 O 4 Solution), mixing and stirring, and centrifuging after 6 hours;
(6) Centrifugally separating solid residues in the step (5) to obtain a mixture of the catalyst and the carbonized residues, performing magnetic separation and drying respectively, wherein the mass of the recovered catalyst is 179g, and the balance of 15.1kg is used as a base fertilizer raw material containing the humic acid compound fertilizer;
(7) The liquid obtained by centrifugal separation in the step (5) is a primary product of the super-mineral humic acid-containing water-soluble fertilizer, and the primary product is concentrated or diluted to obtain a liquid product of the super-mineral humic acid-containing water-soluble fertilizer (macroelement type); then concentrated and granulated to obtain 101kg of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type).
In the embodiment, 100kg of biomass solid waste is treated, the addition amount of a catalyst is 200g, the addition amount of an activating agent is 25kg, the addition amount of an oxidizing agent is about 4kg, and the addition amount of an extracting agent is about 6kg, after the reaction is finished, the concentrated granulation is carried out to obtain 101kg of a super-mineral humic acid-containing water-soluble fertilizer (macroelement type) protective body product, 179g of the catalyst is separated and recycled through magnetic separation, and the total amount of the unrecovered catalyst and unreacted biomass residue is 15.1g.
Table 1 technical index test results of solid product containing super-mineral humic acid water-soluble fertilizer (macroelement type) obtained in example 1
| Item | Results |
| Content of humic acid of super mineral origin% | 56.9 |
| Macro-element content,%) | 2.7 (Total N) +4.2 (P) 2 O 5 )+14.2(K 2 O)＝21.1 |
| Water insoluble content of% | 0.3 |
| pH (1 | 8.7 |
| Water content (H) 2 O)，％ | 3.3 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing a super-mineral humic acid-containing water-soluble fertilizer by utilizing agriculture and forestry biomass solid wastes is characterized by comprising the following steps:
(1) Heating ferric salt at 100-300 deg.c for 6-18 hr to obtain hydroxyl ferric oxide and/or ferric oxide catalyst;
(2) Uniformly mixing the catalyst obtained in the step (1), biomass solid waste powder and an activating agent, roasting at the temperature of between room temperature and 150 ℃ for 1 to 2 hours in an air atmosphere, roasting at the temperature of between 150 and 200 ℃ for 1 to 2 hours with the volume content of oxygen of between 10 and 15 percent, and roasting at the temperature of between 200 and 300 ℃ for 1 to 2 hours with the volume content of oxygen of between 0 and 10 percent to obtain a weatherlike coal precursor;
(3) Mixing the weatherlike coal precursor obtained in the step (2) with an oxidant aqueous solution, activating for 24-72 h at 60-100 ℃, adding the obtained oxidation product into an extractant solution, extracting for 3-6 h, and performing solid-liquid separation;
(4) Magnetically separating the solid residue obtained in the step (3) to recover the catalyst, and taking the rest as a base fertilizer raw material containing the humic acid compound fertilizer;
(5) And (4) concentrating and granulating the liquid obtained in the step (3) to obtain a liquid product of the super-mineral humic acid-containing water-soluble fertilizer, namely a solid product of the super-mineral humic acid-containing water-soluble fertilizer.
2. The method of claim 1, wherein the ferric salt in step (1) is at least one of ferric chloride, ferric nitrate and ferric sulfate; the dosage of the catalyst in the step (2) is 0.05-1% of the mass of the biomass solid waste powder.
3. The method according to claim 2, wherein the amount of the catalyst used in the step (2) is 0.2-0.5% of the mass of the biomass solid waste powder.
4. The method according to claim 1, wherein the ferric salt in step (1) is subjected to hydrothermal reaction at 100-200 ℃ to obtain ferric hydroxide; carrying out hydrothermal reaction at 200-300 ℃ to obtain the ferric oxide.
5. The method of claim 1, wherein the activating agent of step (2) is K 3 PO 4 、K 2 HPO 4 、KH 2 PO 4 、KNO 3 、KNO 2 And K 2 CO 3 At least one of; the dosage of the activating agent is 10-50% of the mass of the biomass solid waste powder.
6. The method of claim 1, wherein the oxidant in the aqueous oxidant solution of step (3) is KMnO 4 、H 2 O 2 、HNO 3 、CH 3 COOOH and (NH) 4 ) 2 S 2 O 8 At least one of (a); the using amount of the oxidant is 1-10% of the mass of the biomass solid waste powder in the step (2);
the mass fraction of the oxidant aqueous solution in the step (3) is 0.5-5%.
7. The method of claim 1, wherein in the solution of the extractant in step (3), the extractant is KOH or K 2 CO 3 、K 4 P 2 O 7 And K 2 C 2 O 4 At least one of; the dosage of the extractant is 2-20% of the mass of the biomass solid waste powder in the step (2);
the mass fraction of the extractant solution in the step (3) is 1-10%.
8. The method as claimed in claim 1, wherein the particle size of the biomass solid waste powder in the step (2) is less than or equal to 0.150mm; and (3) the biomass solid waste powder raw material in the step (2) is at least one of cotton stalks, rice hulls and trees.
9. The method according to claim 1, wherein the amount of the activating agent in the step (2) is 25-30% of the mass of the biomass solid waste powder; the using amount of the oxidant is 4% of the mass of the biomass solid waste powder in the step (2); the dosage of the extraction agent is 6% of the mass of the biomass solid waste powder in the step (2).
10. The method according to claim 1, wherein the liquid product of the water-soluble fertilizer containing the humic acid of the super mineral source in the step (5) is concentrated or diluted to be used as a water-soluble fertilizer; the concentration granulation adopts a concentration granulation process combining triple effect evaporation and spray drying process.
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