CN116514611A - Method for producing fulvic acid fertilizer by agricultural wastes in cooperation - Google Patents
Method for producing fulvic acid fertilizer by agricultural wastes in cooperation Download PDFInfo
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- CN116514611A CN116514611A CN202310796695.8A CN202310796695A CN116514611A CN 116514611 A CN116514611 A CN 116514611A CN 202310796695 A CN202310796695 A CN 202310796695A CN 116514611 A CN116514611 A CN 116514611A
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- fulvic acid
- purity
- residue
- fermentation
- saccharification
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- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 title claims abstract description 96
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000002509 fulvic acid Substances 0.000 title claims abstract description 96
- 229940095100 fulvic acid Drugs 0.000 title claims abstract description 96
- 239000003337 fertilizer Substances 0.000 title claims abstract description 66
- 239000002154 agricultural waste Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000000034 method Methods 0.000 claims abstract description 96
- 239000000463 material Substances 0.000 claims abstract description 83
- 238000000855 fermentation Methods 0.000 claims abstract description 67
- 230000004151 fermentation Effects 0.000 claims abstract description 67
- 239000010902 straw Substances 0.000 claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920005610 lignin Polymers 0.000 claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 240000008042 Zea mays Species 0.000 claims description 107
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 107
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 106
- 235000005822 corn Nutrition 0.000 claims description 106
- 238000009264 composting Methods 0.000 claims description 61
- 239000002361 compost Substances 0.000 claims description 60
- 239000002994 raw material Substances 0.000 claims description 42
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 34
- 239000007800 oxidant agent Substances 0.000 claims description 27
- 241000194108 Bacillus licheniformis Species 0.000 claims description 26
- 244000063299 Bacillus subtilis Species 0.000 claims description 26
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 26
- 241000223261 Trichoderma viride Species 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- 240000006439 Aspergillus oryzae Species 0.000 claims description 25
- 235000002247 Aspergillus oryzae Nutrition 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 238000009423 ventilation Methods 0.000 claims description 20
- 230000001590 oxidative effect Effects 0.000 claims description 19
- 241000233866 Fungi Species 0.000 claims description 18
- 108010029541 Laccase Proteins 0.000 claims description 15
- 239000002054 inoculum Substances 0.000 claims description 15
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 14
- 241000222393 Phanerochaete chrysosporium Species 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 230000007423 decrease Effects 0.000 claims description 12
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 9
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 9
- 108090000790 Enzymes Proteins 0.000 claims description 8
- 102000004190 Enzymes Human genes 0.000 claims description 8
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002068 microbial inoculum Substances 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 241000123346 Chrysosporium Species 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 21
- 230000003647 oxidation Effects 0.000 abstract description 19
- 230000000813 microbial effect Effects 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 235000015097 nutrients Nutrition 0.000 abstract description 8
- 239000003895 organic fertilizer Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 229920002678 cellulose Polymers 0.000 abstract description 6
- 239000001913 cellulose Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 230000013595 glycosylation Effects 0.000 abstract description 3
- 238000006206 glycosylation reaction Methods 0.000 abstract description 3
- 235000021049 nutrient content Nutrition 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 239000002893 slag Substances 0.000 description 12
- 230000007704 transition Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 6
- 238000010564 aerobic fermentation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007226 seed germination Effects 0.000 description 4
- 238000009629 microbiological culture Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 241000228212 Aspergillus Species 0.000 description 1
- 241000395107 Cladosporium cucumerinum Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 101150096185 PAAS gene Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/20—Preparation 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
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/50—Treatments combining two or more different biological or biochemical treatments, e.g. anaerobic and aerobic treatment or vermicomposting and aerobic treatment
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Abstract
The invention relates to the technical field of agricultural waste recycling, in particular to a method for cooperatively producing fulvic acid fertilizer by using agricultural waste. The invention combines the microbial fermentation method and the chemical catalytic oxidation method to produce the fulvic acid organic fertilizer, and can simultaneously play the role of green decomposition of cellulose, lignin and high-efficiency synthesis of fulvic acid by the chemical catalytic oxidation method; the straw glycosylation residue and the biogas residue are utilized to carry out mixed fulvic acid fermentation, so that the utilization residue of agricultural wastes can be effectively utilized, and the resource potential of the agricultural wastes such as straw and the like can be fully utilized; the disintegration of lignocellulose and the synthesis of fulvic acid are effectively promoted through temperature gradient change and pressure transformation and pressure relief in the catalytic oxidation process, so that the yield of fulvic acid is improved; the N nitrogen in the biogas residue is utilized to supplement the nutrient balance of the material, and the nutrient content of the fulvic acid fertilizer is adjusted, so that other mineral fertilizers are not required to be mixed when the fulvic acid fertilizer is applied, and the problems of low efficiency, high energy consumption, poor fertilizer quality and the like in the preparation of the fulvic acid fertilizer by agricultural wastes are solved.
Description
Technical Field
The invention relates to the technical field of agricultural waste recycling, in particular to a method for cooperatively producing fulvic acid fertilizer by using agricultural waste.
Background
The comprehensive production capacity of agriculture in China is continuously improved, the scale and industrialization degree are continuously improved, the yield of crops and agricultural products is continuously improved, and the agricultural wastes are continuously increased. Straw is a lignocellulose biomass with rich sources, and is one of main agricultural wastes. The saccharification of the straw, which utilizes cellulose and hemicellulose to produce five-carbon sugar and six-carbon sugar, is an important step for producing polylactic acid and fuel ethanol by high-value utilization of the straw. The sugar slag has higher lignin content, so that fulvic acid can be produced, and the full and efficient utilization of lignocellulose biomass raw materials is realized. The fulvic acid molecule has benzene rings and various heterocyclic structures, contains more active groups such as carboxyl, hydroxyl, amido and the like, has stronger ion exchange, complexing and adsorption capacities, can effectively improve the soil structure, and has been popularized and applied in agricultural production.
At present, two methods exist for producing plant source fulvic acid: firstly, the microbial fermentation method is to convert organic matters into humic acid active substances including Biochemical Fulvic Acid (BFA) under the combined action of a plurality of microorganisms. The prior art researches the nitrogen source type, the straw crushing degree, the fermentation process temperature, the water content, the pH and the microbial quantity change in the aerobic fulvic acid fermentation; and screening the strain producing fulvic acid by using the corn straw. The enhancement is usually carried out by inoculating lignin-decomposing enzymes such as exogenous microbial agents or laccase, but the microbial fermentation takes longer time and the production rate is lower. Secondly, a chemical method is adopted, a catalyst and an oxidant are added to carry out chemical decomposition at high temperature to prepare the Oxidized Fulvic Acid (OFA), the preparation rate is high, the energy input is high, the application is wide in production, but the fulvic acid fertilizer produced by the chemical method is unbalanced in nutrient, and other mineral fertilizers are required to be mixed for subsequent utilization.
Disclosure of Invention
In order to solve the problems, the invention provides a method for cooperatively producing fulvic acid fertilizer by agricultural wastes. The method provided by the invention mainly utilizes the mixed raw materials of the sugar-making residues of agricultural wastes (straws) and the biogas residues of biogas engineering, combines a microbial fermentation method with a chemical catalytic oxidation method, uses the biogas residues as a nitrogen source, adjusts the nutrient balance of materials, improves the production efficiency of fulvic acid, reduces the energy consumption, improves the nutrient balance of fulvic acid fertilizer, fully exerts the production potential of the agricultural wastes, and improves the economic benefit.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for cooperatively producing fulvic acid fertilizer by agricultural wastes, which comprises the following steps:
mixing the corn stalk saccharification residues with biogas residues to obtain fermentation materials; the corn stalk saccharification residues comprise high-purity corn stalk saccharification residues or low-purity corn stalk saccharification residues; the total lignin content of the high-purity corn straw saccharification residues is 60-70 wt%; the total lignin content of the low-purity corn straw saccharification residues is 20-30 wt.%; the total nitrogen content of the biogas residue is 1wt.% to 1.5wt.%;
mixing the fermentation material with a fermentation microbial inoculum to obtain a compost raw material; when the corn stalk saccharification residue is a high-purity corn stalk saccharification residue, the fermentation inoculant comprises laccase and white rot fungi (Phanerochaetc chrysosporium); when the corn stalk saccharification residue is a low-purity corn stalk saccharification residue, the fermentation inoculant comprises bacillus subtilis (Bacillus subtilis), bacillus licheniformis (Bacillus licheniformis), trichoderma viride (Trichoderma viride) and aspergillus oryzae (Aspergillus oryzae); the ratio of the viable count of the bacillus subtilis, the bacillus licheniformis, the trichoderma viride and the aspergillus oryzae is 1:1:2:1.5;
continuously aerobic composting is carried out on the composting raw materials to obtain primary compost; the material retention time of the continuous aerobic composting is 7-9 days; when the corn stalk saccharification residue is high-purity corn stalk saccharification residue, the conditions of the continuous microaerobic composting include: the positive pressure ventilation rate is 0.08-0.1L/(min.kg); when the corn straw saccharification residue is low-purity corn straw saccharification residue, the continuous aerobic composting method comprises the following steps: the positive pressure ventilation rate is reduced from 0.2-0.24L/(min.kg) step by step to 0.08-0.12L/(min.kg) from the feeding direction of the compost raw material to the primary compost generation direction; the number of step decreases is 3, and the positive pressure ventilation rate of each decrease is 0.04L/(min.kg);
mixing the primary compost, the catalyst and the oxidant to obtain a mixed material; the catalyst comprises ammonium sulfite; the oxidizing agent comprises ferric oxide and/or manganese dioxide;
carrying out 3 times of catalytic oxidation reaction on the mixed material to obtain the fulvic acid fertilizer; the method for each catalytic oxidation reaction comprises the following steps: 1) Reacting for 4 hours under the condition that the initial heating temperature is 95 ℃ and the pressure is 0.1 MPa; 2) Heating to 100 ℃, and reacting for 4 hours under the conditions of 100 ℃ and 0.3MPa, wherein the pressure is increased to 0.3 MPa; 3) Heating to 105 ℃, and reacting for 4 hours under the conditions of 105 ℃ and 0.6MPa, wherein the pressure is increased to 0.6 MPa; 4) Decompression to 0.1MPa, stopping heating, and cooling to 95 ℃.
Preferably, the white rot fungi include Phanerochaete chrysosporium (Phanerochaete chrysosporium Burdsall); the preservation number of the Phanerochaete chrysosporium is CGMCC 3.7212; the preservation number of the bacillus subtilis is CGMCC 1.15792; the preservation number of the bacillus licheniformis is CGMCC 1.6510; the preservation number of the trichoderma viride is CGMCCThe method comprises the steps of carrying out a first treatment on the surface of the The preservation number of the Aspergillus oryzae is CGMCC +.>。
Preferably, the water content of the fermentation material is 50% -55%; the pH value of the fermentation material is 6.5-7.5; the carbon-nitrogen ratio of the fermentation material is (25-30): 1.
preferably, the composting raw material further comprises sodium polyacrylate; the mass ratio of the sodium polyacrylate to the fermentation material is (0.5-1): 100.
preferably, when the corn stalk saccharification residue is high-purity corn stalk saccharification residue, the mass ratio of the white rot fungi to the fermentation material is (2-3): 1000, wherein the mass ratio of laccase to fermentation material is (1.5-2): 1000; effective viable count of the white rot fungi>1.4×10 9 CFU/g; the enzyme activity of the laccase is more than or equal to 0.5U/mg;
when the corn straw saccharification residue is low-purity corn straw saccharification residue, the mass ratio of the fermentation microbial inoculum to the fermentation material is (2-3): 1000; effective viable count of the fermentation inoculant>2×10 9 CFU/g。
Preferably, the mass ratio of the ammonium sulfite to the primary compost is (10-15): 100; the mass ratio of the ferric oxide to the primary compost is (1.0-1.5): 100; the mass ratio of the manganese dioxide to the primary compost is (1.5-2.0): 100.
preferably, after the primary compost, the catalyst and the oxidant are mixed, the method further comprises the step of standing the mixture for 0.5-1 day.
Preferably, the high-purity corn straw saccharification residues are high-purity lignin sugar residues obtained by alkali liquor recovery after kneading-dilute alkali pretreatment in the corn straw biochemical production process; the low-purity corn straw saccharification residue is low-purity lignin saccharification residue obtained after the corn straw biochemical production process is subjected to kneading-dilute alkali pretreatment and the solid and liquid two-step enzymolysis to produce sugar.
The invention also provides a fulvic acid fertilizer which is prepared by the preparation method of the technical scheme.
The beneficial effects are that:
the invention provides a method for cooperatively producing fulvic acid fertilizer by agricultural wastes, which comprises the following steps: mixing the corn stalk saccharification residues with biogas residues to obtain fermentation materials; the corn stalk saccharification residues comprise high-purity corn stalk saccharification residues or low-purity corn stalk saccharification residues; the total lignin content of the high-purity corn straw saccharification residues is 60-70 wt%; the total lignin content of the low-purity corn straw saccharification residues is 20-30 wt.%; the total nitrogen content of the biogas residue is 1wt.% to 1.5wt.%; mixing the fermentation material with a fermentation microbial inoculum to obtain a compost raw material; when the corn stalk saccharification residue is a high-purity corn stalk saccharification residue, the fermentation inoculant comprises laccase and white rot fungi (Phanerochaetc chrysosporium); when the corn stalk saccharification residue is a low-purity corn stalk saccharification residue, the fermentation inoculant comprises bacillus subtilis (Bacillus subtilis), bacillus licheniformis (Bacillus licheniformis), trichoderma viride (Trichoderma viride) and aspergillus oryzae (Aspergillus oryzae); the ratio of the viable count of the bacillus subtilis, the bacillus licheniformis, the trichoderma viride and the aspergillus oryzae is 1:1:2:1.5; continuously aerobic composting is carried out on the composting raw materials to obtain primary compost; the material retention time of the continuous aerobic composting is 7-9 days; when the corn stalk saccharification residue is high-purity corn stalk saccharification residue, the conditions of the continuous microaerobic composting include: the positive pressure ventilation rate is 0.08-0.1L/(min.kg); when the corn straw saccharification residue is low-purity corn straw saccharification residue, the continuous aerobic composting method comprises the following steps: the positive pressure ventilation rate is reduced from 0.2-0.24L/(min.kg) step by step to 0.08-0.12L/(min.kg) from the feeding direction of the compost raw material to the primary compost generation direction; the number of step decreases is 3, and the positive pressure ventilation rate of each decrease is 0.04L/(min.kg); mixing the primary compost, the catalyst and the oxidant to obtain a mixed material; the catalyst comprises ammonium sulfite; the oxidizing agent comprises ferric oxide and/or manganese dioxide; carrying out 3 times of catalytic oxidation reaction on the mixed material to obtain the fulvic acid fertilizer; the method for each catalytic oxidation reaction comprises the following steps: 1) Reacting for 4 hours under the condition that the initial heating temperature is 95 ℃ and the pressure is 0.1 MPa; 2) Heating to 100 ℃, and reacting for 4 hours under the conditions of 100 ℃ and 0.3MPa, wherein the pressure is increased to 0.3 MPa; 3) Heating to 105 ℃, and reacting for 4 hours under the conditions of 105 ℃ and 0.6MPa, wherein the pressure is increased to 0.6 MPa; 4) Decompression to 0.1MPa, stopping heating, and cooling to 95 ℃. The invention combines the microbial fermentation method and the chemical catalytic oxidation method to produce the fulvic acid organic fertilizer, and can simultaneously play the role of green decomposition of cellulose, lignin and high-efficiency synthesis of fulvic acid by the chemical catalytic oxidation method; different conditions are respectively adopted in the aerobic composting process according to different total lignin contents, and the aerobic composting process is changed from aerobic to micro-aerobic fermentation gradually through the regulation and control of the aeration rate aiming at the low-purity corn straw saccharification residues as raw materials, so that the energy consumption is reduced, the balance stability of microbial communities is maintained, and the high-temperature period of the composting is prolonged; aiming at the aerobic composting with high-purity corn straw saccharification residues as raw materials, the fixed micro-aerobic fermentation is adopted, so that the oxygen utilization rate can be remarkably improved, the fixation and the maintenance of nitrogen are promoted, the nitrogen loss is reduced, and the humification process is accelerated; aiming at corn straw glycosylated residues with different lignin contents, different bactericides, laccase and white rot fungi can rapidly decompose lignin, so that the decomposition rate of high lignin raw materials is improved; the mixed microbial inoculum of the bacillus subtilis, the bacillus licheniformis, the trichoderma viride and the aspergillus oryzae can comprehensively utilize macromolecules such as starch, protein, cellulose, lignin and the like in raw materials, and improves the full-component decomposition process. Meanwhile, the high temperature of the aerobic compost can greatly reduce the heating energy consumption from room temperature to 95 ℃ directly, and has the advantage of low energy consumption; furthermore, the straw glycosylation residue and the biogas residue are utilized to carry out mixed fulvic acid fermentation, so that the utilization residue of agricultural wastes can be effectively utilized, and the resource potential of the agricultural wastes such as straw and the like can be fully exerted; the catalytic oxidation process adopts a variable temperature and pressure mode, and the disintegration of lignocellulose and the synthesis of fulvic acid are effectively promoted through temperature gradient change and pressure transformation and pressure relief, so that the yield of fulvic acid is improved; the N nitrogen in the biogas residue is utilized to supplement the nutrient balance of the material, and the nutrient content of the fulvic acid fertilizer is adjusted, so that other mineral fertilizers are not required to be mixed when the fulvic acid fertilizer is applied, and the problems of low efficiency, high energy consumption, poor fertilizer quality and the like in the preparation of the fulvic acid fertilizer by agricultural wastes are solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments will be briefly described below.
FIG. 1 is a schematic diagram of a method and a device for cooperatively producing fulvic acid fertilizer by high-purity corn straw saccharification residues and biogas residues;
FIG. 2 is a schematic diagram of a method and a device for cooperatively producing fulvic acid fertilizer from saccharification residues and biogas residues of low-purity corn stalks;
FIG. 3 is a flow chart of a method for cooperatively producing fulvic acid fertilizer by agricultural wastes.
Detailed Description
The invention provides a method for cooperatively producing fulvic acid fertilizer by agricultural wastes, which comprises the following steps:
mixing the corn stalk saccharification residues with biogas residues to obtain fermentation materials; the corn stalk saccharification residues comprise high-purity corn stalk saccharification residues or low-purity corn stalk saccharification residues; the total lignin content of the high-purity corn straw saccharification residues is 60-70 wt%; the total lignin content of the low-purity corn straw saccharification residues is 20-30 wt.%; the total nitrogen content of the biogas residue is 1wt.% to 1.5wt.%;
mixing the fermentation material with a fermentation microbial inoculum to obtain a compost raw material; when the corn stalk saccharification residue is a high-purity corn stalk saccharification residue, the fermentation inoculant comprises laccase and white rot fungi (Phanerochaetc chrysosporium); when the corn stalk saccharification residue is a low-purity corn stalk saccharification residue, the fermentation inoculant comprises bacillus subtilis (Bacillus subtilis), bacillus licheniformis (Bacillus licheniformis), trichoderma viride (Trichoderma viride) and aspergillus oryzae (Aspergillus oryzae); the ratio of the viable count of the bacillus subtilis, the bacillus licheniformis, the trichoderma viride and the aspergillus oryzae is 1:1:2:1.5;
continuously aerobic composting is carried out on the composting raw materials to obtain primary compost; the material retention time of the continuous aerobic composting is 7-9 days; when the corn stalk saccharification residue is high-purity corn stalk saccharification residue, the conditions of the continuous microaerobic composting include: the positive pressure ventilation rate is 0.08-0.1L/(min.kg); when the corn straw saccharification residue is low-purity corn straw saccharification residue, the continuous aerobic composting method comprises the following steps: the positive pressure ventilation rate is reduced from 0.2-0.24L/(min.kg) step by step to 0.08-0.12L/(min.kg) from the feeding direction of the compost raw material to the primary compost generation direction; the number of step decreases is 3, and the positive pressure ventilation rate of each decrease is 0.04L/(min.kg);
mixing the primary compost, the catalyst and the oxidant to obtain a mixed material; the catalyst comprises ammonium sulfite; the oxidizing agent comprises ferric oxide and/or manganese dioxide;
carrying out 3 times of catalytic oxidation reaction on the mixed material to obtain the fulvic acid fertilizer; the method for each catalytic oxidation reaction comprises the following steps: 1) Reacting for 4 hours under the condition that the initial heating temperature is 95 ℃ and the pressure is 0.1 MPa; 2) Heating to 100 ℃, and reacting for 4 hours under the conditions of 100 ℃ and 0.3MPa, wherein the pressure is increased to 0.3 MPa; 3) Heating to 105 ℃, and reacting for 4 hours under the conditions of 105 ℃ and 0.6MPa, wherein the pressure is increased to 0.6 MPa; 4) Decompression to 0.1MPa, stopping heating, and cooling to 95 ℃.
According to the invention, corn straw saccharification residues and biogas residues are mixed to obtain fermentation materials. In the invention, the corn stalk saccharification residues preferably comprise saccharification residues of different stages obtained by carrying out kneading-dilute alkali pretreatment and enzymolysis and sugar production on corn stalks by a two-step method, namely high-purity corn stalk saccharification residues (namely high-purity lignin sugar residues in the figure 1) and low-purity corn stalk saccharification residues (namely low-purity lignin sugar residues in the figure 2); the high-purity corn straw saccharification residues are preferably high-purity lignin sugar residues obtained by alkali liquor recovery after kneading-dilute alkali pretreatment in the corn straw biochemical production process; the low-purity corn straw saccharification residues are preferably low-purity lignin saccharification residues obtained after the corn straw biochemical production process is subjected to kneading-dilute alkali pretreatment and the sugar is produced by enzymolysis of solid and liquid in two steps; the total lignin content of the high-purity corn straw saccharification residues is preferably 60-70 wt.%, more preferably 70wt.%; the total lignin content of the low-purity corn straw saccharification residues is preferably 20-30 wt.%, more preferably 30wt.%; the total nitrogen content of the biogas residue is preferably 1wt.% to 1.5wt.%, and more preferably 1.5wt.%.
The invention has no special requirement on the source of the biogas residue, and can meet the total nitrogen content limited by the technical scheme.
According to the invention, after corn straw saccharification residues and biogas residues are mixed, the water content, pH value and carbon nitrogen ratio of the mixed materials are preferably adjusted to obtain the fermentation material. In the invention, the mass ratio of the corn stalk saccharification residue to the biogas residue is preferably 3: (2-1), more preferably 3:2; the water content of the mixed material is preferably 50% -55%, more preferably 55%; the pH value of the mixed material is preferably 6.5-7.5, more preferably 7.0-7.5; the carbon-nitrogen ratio of the mixed materials is preferably (25-30): 1, more preferably 30:1.
the invention utilizes the mixed maize straw glycosylation residue and biogas residue to ferment fulvic acid, can effectively utilize the utilization residue of agricultural wastes, and fully exert the resource potential of the agricultural wastes such as straw and the like. The nutrient balance of the materials is supplemented by nitrogen in the biogas residues, and the nutrient content of the fulvic acid fertilizer is adjusted, so that other mineral fertilizers are not required to be mixed when the fulvic acid fertilizer is applied. The fulvic acid content in the fulvic acid fertilizer prepared by taking the high-purity corn straw saccharification residues as raw materials is 60-70 wt.%, the organic matter content is 50-55 wt.%, the germination index of seeds is more than 85%, and the total nitrogen content is 9.0-9.7 g/kg; the fulvic acid fertilizer prepared from the low-purity corn straw saccharification residues is 30-40 wt.%, the organic matter content is 45-50 wt.%, the seed germination index is more than 80%, and the total nitrogen content is 9.0-9.7 g/kg.
After the fermentation material is obtained, the invention mixes the fermentation material and the fermentation inoculant to obtain the compost raw material.
When the fermentation material contains high-purity corn stalk saccharification residues, namely the fermentation material comprises high-purity corn stalk saccharification residues and biogas residues, the fermentation inoculant comprises laccase and white rot fungi (Phanerochaetc chrysosporium). The white rot fungi of the invention preferably comprise Phanerochaete chrysosporium (Phanerochaete chrysosporium Burdsall); the white rot fungi and the quality of the fermented materialThe preferred amount ratio is (2-3): 1000, more preferably 2:1000; the effective viable count of the white rot fungi is preferably>1.4×10 9 CFU/g; the mass ratio of laccase to fermentation material is preferably (1.5-2): 1000, more preferably 2:1000; the enzyme activity of laccase is preferably more than or equal to 0.5U/mg; the 1 enzyme activity unit (U) corresponds to the amount of enzyme required to convert 1. Mu.M catechol per minute at pH5.0 and 25 ℃. The Phanerochaete chrysosporium is preferably purchased from China general microbiological culture Collection center, and the preservation number is preferably CGMCC 3.7212. The invention selects proper amount of laccase and white rot fungi as the fermentation inoculant of high-purity corn straw saccharification residues, can utilize the characteristics of enzyme and microorganism degradation lignin, improves lignin degradation rate, improves material utilization efficiency, and further improves the content of fulvic acid in the product.
When the fermentation material contains low-purity corn stalk saccharification residues, namely the fermentation material comprises the low-purity corn stalk saccharification residues and biogas residues, the fermentation inoculant comprises bacillus subtilis (Bacillus subtilis), bacillus licheniformis (Bacillus licheniformis), trichoderma viride (Trichoderma viride) and aspergillus oryzae (Aspergillus oryzae); the ratio of the viable count of the bacillus subtilis, the bacillus licheniformis, the trichoderma viride and the aspergillus oryzae is 1:1:2:1.5.
in the present invention, the total effective viable count of the Bacillus subtilis, bacillus licheniformis, trichoderma viride and Aspergillus oryzae is preferably>2×10 9 CFU/g; the mass ratio of the fermentation inoculant to the fermentation material is (2-3): 1000, more preferably 3:1000; the bacillus subtilis, the bacillus licheniformis, the trichoderma viride and the aspergillus oryzae are preferably purchased from China general microbiological culture collection center; the preservation number of the bacillus subtilis is preferably CGMCC 1.15792; the preservation number of the bacillus licheniformis is preferably CGMCC 1.6510; the preservation number of the trichoderma viride is preferably CGMCCThe method comprises the steps of carrying out a first treatment on the surface of the The preservation number of the aspergillus oryzae is preferably CGMCC +.>。
The microbial agent obtained by compounding the proper bacillus subtilis, bacillus licheniformis, trichoderma viride and aspergillus oryzae is selected as the fermentation microbial agent of the high-purity corn straw saccharification residues, so that the starch, protein, cellulose and lignin in the fermentation materials can be comprehensively utilized, and the decomposition rate is improved.
In the present invention, the composting material preferably further comprises sodium Polyacrylate (PAAS); the mass ratio of the sodium polyacrylate to the fermentation material is preferably (0.5-1): 100, more preferably 1:100.
the invention can promote the composting reaction process and reduce NH by adding proper sodium polyacrylate as a compost conditioner in the compost 3 Volatilizing, reducing nitrogen loss in the composting process.
After the compost raw material is obtained, the invention carries out continuous aerobic composting on the compost raw material to obtain primary compost.
As shown in fig. 1 and 2, the steps from the time of obtaining the compost raw material to the time of obtaining the fulvic acid fertilizer are preferably performed in a continuous dynamic aerobic composting reactor, and the continuous dynamic aerobic composting reactor is preferably subjected to functional partitioning, preferably comprising a composting functional area, a transition area and a fulvic acid forming area; the continuous dynamic aerobic composting reactor preferably comprises a DANO roller dynamic composting device; the DANO roller dynamic composting apparatus is preferably purchased from New rural Galaxy mechanical Electrical Co., ltd., model HT120028.
The continuous aerobic composting is preferably carried out in a composting functional area; when the corn stalk saccharification residue is high-purity corn stalk saccharification residue, the conditions of the continuous microaerobic composting include: the positive pressure ventilation rate is 0.08-0.1L/(min.kg); when the corn straw saccharification residue is low-purity corn straw saccharification residue, the continuous aerobic composting method comprises the following steps: the positive pressure ventilation rate is reduced from 0.2-0.3L/(min.kg) step by step to 0.08-0.1L/(min.kg) from the feeding direction of the compost raw material to the primary compost generation direction; the number of step decreases is 3, and the positive pressure ventilation rate of each decrease is 0.04L/(min.kg); the material residence time of the continuous aerobic composting is 7-9 days, preferably 9 days.
The method for continuous aerobic composting according to the invention preferably further comprises: adding composting raw materials every 2 days; the material filling rate is preferably 60-70%, more preferably 60%; the reactor speed is preferably 0.3r/min.
In the continuous aerobic composting process, macromolecular organic matters contained in composting raw materials taking low-purity corn straw saccharification residues and biogas residues as main raw materials are depolymerized into substances such as phenol, quinone, reducing sugar, amino acid and the like, and the substances are decomposed into small molecules to generate humic acid precursor substances; the aeration intensity is gradually reduced, so that the energy consumption can be reduced, the microbial community balance is maintained, the activity of facultative anaerobes is improved, the composting temperature is maintained, materials enter a high-temperature period (60-70 ℃) of the compost from the initial stage of the composting, and the high-temperature reaction period lasts for 5-7 days.
After the primary compost is obtained, the invention preferably moves the primary compost to a transition zone and adds a catalyst and an oxidant to obtain a mixed material. The catalyst of the invention comprises ammonium sulfite; the oxidizing agent comprises iron oxide and/or manganese dioxide. In the invention, the addition amount of the catalyst or the oxidant is preferably calculated by primary compost, and the ammonium sulfite accounts for preferably 10-15% of the mass of the primary compost, more preferably 15%; the iron oxide accounts for 1.0% -1.5% of the primary compost by mass, and more preferably 1.5%; the manganese dioxide accounts for 1.5-2.0% of the primary compost by mass, and more preferably 2.0%.
The transition zone separates the composting functional zone from the fulvic acid generating zone, and prevents the high temperature of chemical catalytic oxidation from affecting the activity of composting microorganisms.
In the invention, the residence time of the mixture in the transition zone is preferably 0.5-1 day, more preferably 1 day.
After the mixed material is obtained, the mixed material is moved to a fulvic acid forming area to carry out 3 times of catalytic oxidation reaction, and the fulvic acid fertilizer is obtained.
The catalytic oxidation reaction adopts a temperature and pressure changing mode, and materials are discharged from the system after 3 times of circulation (namely 3 times of catalytic oxidation reaction) are finished; the method for each catalytic oxidation reaction comprises the following steps: initial heating temperature 95 ℃, initial pressure 1 standard atmosphere (i.e. 0.1 MPa); after 4 hours of reaction, the temperature is raised to 100 ℃, and the pressure is raised to 3 standard atmospheric pressures (namely 0.3 MPa) and kept for 4 hours; after 4 hours of storage, the temperature is raised to 105 ℃, the pressure is raised to 6 standard atmospheres (namely 0.6 MPa) for 4 hours, the pressure is released to 1 standard atmosphere, then the heating is stopped, and the temperature is reduced to 95 ℃.
The invention carries out functional partitioning on the continuous dynamic aerobic composting reactor, combines the microbial fermentation method and the chemical catalytic oxidation method to produce the fulvic acid organic fertilizer, and can simultaneously play a role in green decomposition of cellulose, lignin and efficient synthesis of fulvic acid by the chemical catalytic oxidation method. The aerobic composting process is gradually changed from aerobic to micro-aerobic fermentation by regulating and controlling the aeration rate, so that the energy consumption is reduced, the balance stability of a microbial community is maintained, and the high-temperature period of the compost is prolonged. Meanwhile, the high temperature of the aerobic compost can greatly reduce the heating energy consumption from room temperature to high temperature of 100 ℃. The catalytic oxidation process adopts a variable temperature and pressure mode, and the disintegration of lignocellulose and the synthesis of fulvic acid are effectively promoted through temperature gradient change and pressure transformation and pressure relief, so that the yield of fulvic acid is improved.
The invention also provides a fulvic acid fertilizer which is prepared by the preparation method of the technical scheme. According to the advantages of the technical scheme, the fulvic acid fertilizer provided by the invention solves the problems of low efficiency, high energy consumption, poor fertilizer quality and the like in the process of preparing the fulvic acid fertilizer from agricultural wastes.
For further explanation of the present invention, a method for co-producing fulvic acid fertilizer from agricultural waste provided by the present invention will be described in detail with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
The continuous dynamic aerobic composting reactor used in the examples or comparative examples was purchased from new country Galaxy mechanical Electrical Co., ltd., model HT120028.
The composite bacterial agents used in the examples or comparative examples are Bacillus subtilis, bacillus licheniformis, trichoderma viride and Aspergillus oryzaeMould; the ratio of the viable count of the bacillus subtilis, the bacillus licheniformis, the trichoderma viride and the aspergillus oryzae is 1:1:2:1.5; the total effective viable count of the composite microbial inoculum is 3 multiplied by 10 9 CFU/g; the white rot fungi is Phanerochaete chrysosporium, and the effective viable count is 1.4X10 9 CFU/g; the Phanerochaete chrysosporium, the bacillus subtilis, the bacillus licheniformis, the trichoderma viride and the aspergillus oryzae are all purchased from the China general microbiological culture collection center; the preservation number of the Phanerochaete chrysosporium is CGMCC 3.7212; the preservation number of the bacillus subtilis is CGMCC 1.15792; the preservation number of the bacillus licheniformis is CGMCC 1.6510; the preservation number of the trichoderma viride is CGMCCThe method comprises the steps of carrying out a first treatment on the surface of the The preservation number of the aspergillus oryzae is CGMCC。
Example 1
A method for cooperatively producing fulvic acid fertilizer by agricultural wastes comprises the following steps:
1) Mixing high-purity lignin sugar slag (purchased from Anhuifeng Yuan group Co., ltd.) obtained by rubbing and dilute alkali pretreatment of corn stalks with biogas slag (purchased from a certain dairy farm biogas engineering of Sanhe) according to a mass ratio of 3:2, wherein the total lignin content of the sugar slag is 60%, and the total nitrogen content of the biogas slag is 1.5%; adjusting the carbon-nitrogen ratio of the mixed material to be 30:1, adjusting the water content of the mixed material to be 55%, adjusting the pH to be 6.5-7, adding sodium polyacrylate to be 0.5% of the wet weight of the mixed material, adding white rot fungi to be 2 per mill of the fresh weight of the mixed material, adding laccase (the enzyme activity is more than or equal to 0.5U/mg) to be 1.5 per mill of the fresh weight of the mixed material, and mixing to obtain a compost raw material;
2) Adding the compost raw material into a continuous dynamic aerobic fermentation device through a feed inlet, wherein the filling rate of the compost raw material is 60%, and the rotating speed of a reactor is 0.3r/min; the composting raw materials are supplemented once a day, the mixing mode is unchanged, and the filling rate of the materials is kept unchanged;
3) The composting raw material enters a composting functional area to carry out continuous microaerobic composting, the positive pressure ventilation rate is 0.1L/(min.kg), and the residence time is 9 days, so that primary compost is obtained;
4) Moving the primary compost to a transition zone, adding a catalyst and an oxidant into the primary compost in the transition zone, and dynamically mixing, wherein the additives comprise the following concrete components in percentage by mass according to the amount of the supplementary materials: the catalyst is 15% of ammonium sulfite, the oxidant is 1.5% of ferric oxide, and the mixture stays for 1 day to obtain a material containing the additive;
5) Moving the material containing the additive to a fulvic acid generation area, and carrying out catalytic oxidation on the mixed material; the catalytic oxidation adopts a temperature and pressure changing mode, and is specifically as follows: initial heating temperature 95 ℃, initial pressure 1 standard atmosphere (i.e. 0.1 MPa); after 4 hours of reaction, the temperature is raised to 100 ℃, and the pressure is raised to 3 standard atmospheric pressures (namely 0.3 MPa) and kept for 4 hours; after 4 hours of preservation, heating to 105 ℃, simultaneously raising the pressure to 6 standard atmospheres (namely 0.6 MPa) for 4 hours, then decompressing to 1 standard atmosphere, then stopping heating, and lowering the temperature to 95 ℃;
6) And (3) taking the temperature and pressure changing process in the step (5) as a cycle, and circulating for 3 times, and flowing out of a discharge hole to obtain the fulvic acid fertilizer.
Example 2
The only difference of the method for cooperatively producing fulvic acid fertilizer by using agricultural wastes similar to the method in the embodiment 1 is that the mass ratio of the high-purity lignin sugar slag to the biogas residue is 3:1.
example 3
A method for cooperatively producing fulvic acid fertilizer by agricultural wastes comprises the following steps:
1) Mixing low-purity lignin sugar slag (purchased from mixed sugar production of Anhuifeng Yuangroup Co., ltd.) obtained by kneading, dilute alkali pretreatment, enzymolysis saccharification of corn stalks with biogas residue (purchased from) according to a mass ratio of 3:2, wherein the total lignin content of the glycosylated residue is 30%, and the total nitrogen content of the biogas residue is 1.5%; adjusting the carbon-nitrogen ratio of the mixed material to be 25:1, adjusting the water content of the mixed material to be 55%, adjusting the pH to be 7-7.5, adding sodium polyacrylate to 0.5% of the wet weight of the mixed material, adding 3 per mill of the fresh weight of the mixed material, and mixing to obtain a compost raw material;
2) Adding the compost raw material into a continuous dynamic aerobic fermentation device through a feed inlet, wherein the filling rate of the compost raw material is 60%, and the rotating speed of a reactor is 0.3r/min; the composting raw materials are supplemented once a day, the mixing mode is unchanged, and the filling rate of the materials is kept unchanged;
3) The composting raw material enters a composting functional area to carry out continuous aerobic composting, the aeration intensity is gradually reduced along with the direction of pushing flow, the environment is changed from aerobic to microaerophilic, namely, the positive pressure ventilation rate is reduced from 0.24L/(min.kg) to 0.12L/(min.kg); the number of step decreases is 3, and the positive pressure ventilation rate of each decrease is 0.04L/(min.kg); the residence time is 9 days, and primary compost is obtained;
4) Moving the primary compost to a transition zone, adding a catalyst and an oxidant into the primary compost in the transition zone, and dynamically mixing, wherein the additives comprise the following concrete components in percentage by mass according to the amount of the supplementary materials: the catalyst is 15% of ammonium sulfite, the oxidant is 1.5% of ferric oxide, and the mixture stays for 1 day to obtain a material containing the additive;
5) Moving the material containing the additive to a fulvic acid generation area, and carrying out catalytic oxidation on the mixed material; the catalytic oxidation adopts a temperature and pressure changing mode, and is specifically as follows: initial heating temperature 95 ℃, initial pressure 1 standard atmosphere (i.e. 0.1 MPa); after 4 hours of reaction, the temperature is raised to 100 ℃, and the pressure is raised to 3 standard atmospheric pressures (namely 0.3 MPa) and kept for 4 hours; after 4 hours of preservation, heating to 105 ℃, simultaneously raising the pressure to 6 standard atmospheres (namely 0.6 MPa) for 4 hours, then decompressing to 1 standard atmosphere, then stopping heating, and lowering the temperature to 95 ℃;
6) And (3) taking the temperature and pressure changing process in the step (5) as a cycle, and circulating for 3 times, and flowing out of a discharge hole to obtain the fulvic acid fertilizer.
Example 4
The only difference of the method for cooperatively producing fulvic acid fertilizer by using agricultural wastes similar to the method in the embodiment 3 is that the mass ratio of the low-purity lignin sugar slag to the biogas residue is 3:1.
example 5
A method for synergistically producing fulvic acid fertilizer by using agricultural wastes similar to example 1 is different in that ammonium sulfite is a catalyst of 10%.
Example 6
A method for synergistically producing fulvic acid fertilizer by using agricultural wastes similar to example 2 is different in that ammonium sulfite is a catalyst of 10%.
Example 7
A method for synergistically producing fulvic acid fertilizer by using agricultural wastes similar to example 3 is different in that ammonium sulfite is a catalyst of 10%.
Example 8
A method for synergistically producing fulvic acid fertilizer by using agricultural wastes similar to example 4 is different in that ammonium sulfite is a catalyst of 10%.
Example 9
A method for synergistically producing fulvic acid fertilizer by using agricultural wastes similar to example 1 is distinguished in that the oxidant is manganese dioxide.
Example 10
A method for synergistically producing fulvic acid fertilizer from agricultural wastes similar to example 2 is distinguished in that the oxidant is manganese dioxide.
Example 11
A method for synergistically producing fulvic acid fertilizer from agricultural wastes similar to example 3 is distinguished in that the oxidant is manganese dioxide.
Example 12
A method for synergistically producing fulvic acid fertilizer from agricultural wastes similar to example 4 is distinguished in that the oxidizing agent is manganese dioxide.
Example 13
A method for synergistically producing fulvic acid fertilizer from agricultural waste similar to that of example 5 is distinguished in that the oxidant is manganese dioxide.
Example 14
A method for synergistically producing fulvic acid fertilizer from agricultural wastes similar to example 6 is distinguished in that the oxidizing agent is manganese dioxide.
Example 15
A method for synergistically producing fulvic acid fertilizer from agricultural waste similar to example 7 is distinguished in that the oxidant is manganese dioxide.
Example 16
A method for synergistically producing fulvic acid fertilizer from agricultural wastes similar to example 8 is distinguished in that the oxidant is manganese dioxide.
Comparative example 1
A process similar to example 1, the only difference being that the mixture in step 1) is free of biogas residues and the carbon-nitrogen ratio is adjusted with urea.
Comparative example 2
A process similar to example 1, the only difference being that steps 4) and 5) are not carried out and that the residence time of step 3) is 10 days.
Comparative example 3
A process similar to example 1, except that step 6) was not carried out, and the catalytic oxidation in step 5) was carried out at a constant temperature and pressure of 105℃and 0.6MPa for 2 days to obtain a fulvic acid fertilizer, which was discharged from the discharge port.
Comparative example 4
A process similar to that of example 1, the only difference being that the plenum rate in step 3) is 0.3L/(min. Kg).
Comparative example 5
A process similar to example 3 is only distinguished in that the mixture in step 1) is free of biogas residues and the carbon-nitrogen ratio is adjusted with urea.
Comparative example 6
A process similar to example 3, the only difference being that steps 4) and 5) are not carried out, the residence time of step 3) being 10 days.
Comparative example 7
A process similar to example 3, except that step 6) was not performed, and the catalytic oxidation in step 5) was adjusted to react at a constant temperature and constant pressure of 100℃and 0.4MPa for 2 days to obtain a fulvic acid fertilizer, which was discharged from the discharge port.
Comparative example 8
A similar method to example 3 was used, except that the plenum rate was unchanged at 0.3L/(min. Kg).
Comparative application example 1
The fulvic acid content, the total nitrogen content, the organic matter content, the nitrogen element loss rate, the seed germination index and the lignin decomposition rate of the fulvic acid fertilizers prepared in examples 1 to 16 and comparative examples 1 to 8 were measured, wherein the fulvic acid content was measured by a volumetric method, the total nitrogen content was measured by a gas phase molecular absorption spectrometry, the organic matter content was measured by a gravimetric method, the nitrogen element loss rate was calculated by a difference value, the seed germination index was calculated by a seed germination test, the lignin decomposition rate was calculated by a cladosporium cucumerinum measurement method, and the measurement results are shown in table 1.
TABLE 1 determination results of different indices of different fulvic acid fertilizers
As can be seen from Table 1, the sugar residues (comparative example 1 and comparative example 5) are adopted independently, the fulvic acid content of the obtained organic fertilizer is 50% and 30%, and the total nitrogen content of the organic fertilizer is only 6.2g/kg and 5.0g/kg; the raw materials adopt glycosylated slag and biogas slag, but only carry out 10 days of aerobic composting (comparative example 2 and comparative example 6), the fulvic acid content of the organic fertilizer is 45 percent and 32 percent respectively, the organic matter content is 40 percent, the total nitrogen content is obviously reduced compared with the example 1, and the total nitrogen content is 6.5g/kg and 5.5g/kg respectively; the raw materials adopt glycosylated slag and biogas slag, but constant temperature and constant pressure are adopted in the catalytic oxidation process (comparative example 3 and comparative example 7), the content of fulvic acid in the organic fertilizer is 44% and 28% respectively, and the energy consumption of the system is 2.5-2.8 times more than that of the method of the invention; the nitrogen loss rate of the compost (comparative example 4 and comparative example 8) with the ventilation rate kept unchanged is 43% -44%, and the lignin decomposition rate is 40% and 20%; under microaerophilic conditions (example 1) and ventilation rate step-down conditions (example 3), the loss rate of nitrogen element is 38.5% -40%, the lignin decomposition rate is 30% -55%, bacterial diversity is increased, and the microbial stability of the system is improved. The use of manganese dioxide (examples 9-16) and iron oxide (examples 1-8) as the oxidizing agent did not significantly affect lignin decomposition rate and product quality, and the fulvic acid content in both cases was significantly higher than in comparative examples 1-8. In summary, the method provided by the invention mainly utilizes the mixed raw materials of the sugar-making residues of agricultural wastes (straws) and the biogas residues of biogas engineering, combines the microbial fermentation method with the chemical catalytic oxidation method, uses the biogas residues as a nitrogen source, adjusts the nutrient balance of materials, improves the production efficiency of fulvic acid, reduces the energy consumption, improves the nutrient balance of fulvic acid fertilizer, fully exerts the production potential of the agricultural wastes, and improves the economic benefit.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (9)
1. The method for producing the fulvic acid fertilizer by utilizing the agricultural wastes is characterized by comprising the following steps of:
mixing the corn stalk saccharification residues with biogas residues to obtain fermentation materials; the corn stalk saccharification residues comprise high-purity corn stalk saccharification residues or low-purity corn stalk saccharification residues; the total lignin content of the high-purity corn straw saccharification residues is 60-70 wt%; the total lignin content of the low-purity corn straw saccharification residues is 20-30 wt.%; the total nitrogen content of the biogas residue is 1wt.% to 1.5wt.%;
mixing the fermentation material with a fermentation microbial inoculum to obtain a compost raw material; when the corn stalk saccharification residue is a high-purity corn stalk saccharification residue, the fermentation inoculant comprises laccase and white rot fungi (Phanerochaetc chrysosporium); when the corn stalk saccharification residue is a low-purity corn stalk saccharification residue, the fermentation inoculant comprises bacillus subtilis (Bacillus subtilis), bacillus licheniformis (Bacillus licheniformis), trichoderma viride (Trichoderma viride) and aspergillus oryzae (Aspergillus oryzae); the ratio of the viable count of the bacillus subtilis, the bacillus licheniformis, the trichoderma viride and the aspergillus oryzae is 1:1:2:1.5;
continuously aerobic composting is carried out on the composting raw materials to obtain primary compost; the material retention time of the continuous aerobic composting is 7-9 days; when the corn stalk saccharification residue is high-purity corn stalk saccharification residue, the conditions of the continuous microaerobic composting include: the positive pressure ventilation rate is 0.08-0.12L/(min.kg); when the corn straw saccharification residue is low-purity corn straw saccharification residue, the continuous aerobic composting method comprises the following steps: the positive pressure ventilation rate is reduced from 0.2-0.24L/(min.kg) step by step to 0.08-0.12L/(min.kg) from the feeding direction of the compost raw material to the primary compost generation direction; the number of step decreases is 3, and the positive pressure ventilation rate of each decrease is 0.04L/(min.kg);
mixing the primary compost, the catalyst and the oxidant to obtain a mixed material; the catalyst comprises ammonium sulfite; the oxidizing agent comprises ferric oxide and/or manganese dioxide;
carrying out 3 times of catalytic oxidation reaction on the mixed material to obtain the fulvic acid fertilizer; the method for each catalytic oxidation reaction comprises the following steps: 1) Reacting for 4 hours under the condition that the initial heating temperature is 95 ℃ and the pressure is 0.1 MPa; 2) Heating to 100 ℃, and reacting for 4 hours under the conditions of 100 ℃ and 0.3MPa, wherein the pressure is increased to 0.3 MPa; 3) Heating to 105 ℃, and reacting for 4 hours under the conditions of 105 ℃ and 0.6MPa, wherein the pressure is increased to 0.6 MPa; 4) Decompression to 0.1MPa, stopping heating, and cooling to 95 ℃.
2. The method of claim 1, wherein the white rot fungi comprises phanerochaete chrysosporium (Phanerochaete chrysosporium Burdsall); the preservation number of the Phanerochaete chrysosporium is CGMCC 3.7212; the preservation number of the bacillus subtilis is CGMCC 1.15792; the preservation number of the bacillus licheniformis is CGMCC 1.6510; the preservation number of the trichoderma viride is CGMCCThe method comprises the steps of carrying out a first treatment on the surface of the The preservation number of the aspergillus oryzae is CGMCC。
3. The method of claim 1, wherein the water content of the fermentation material is 50% -55%; the pH value of the fermentation material is 6.5-7.5; the carbon-nitrogen ratio of the fermentation material is (25-30): 1.
4. the method of claim 1, wherein the composting raw material further comprises sodium polyacrylate; the mass ratio of the sodium polyacrylate to the fermentation material is (0.5-1): 100.
5. the method of claim 1, wherein when the corn straw saccharification residue is a high purity corn straw saccharification residue, the mass ratio of white rot fungi to fermentation material is (2-3): 1000, wherein the mass ratio of laccase to fermentation material is (1.5-2): 1000; effective viable count of the white rot fungi>1.4×10 9 CFU/g; the enzyme activity of the laccase is more than or equal to 0.5U/mg;
when the corn straw saccharification residue is low-purity corn straw saccharification residue, the mass ratio of the fermentation microbial inoculum to the fermentation material is (2-3): 1000; effective viable count of the fermentation inoculant>2×10 9 CFU/g。
6. The method according to claim 1, wherein the mass ratio of the ammonium sulfite to the primary compost is (10-15): 100; the mass ratio of the ferric oxide to the primary compost is (1.0-1.5): 100; the mass ratio of the manganese dioxide to the primary compost is (1.5-2.0): 100.
7. the method of claim 1, further comprising standing the mixture for 0.5 to 1 day after the primary compost, catalyst and oxidant are mixed.
8. The method according to claim 1, wherein the high-purity corn straw saccharification residue is high-purity lignin sugar residue obtained by alkali liquor recovery after kneading-dilute alkali pretreatment in the corn straw biochemical production process; the low-purity corn straw saccharification residue is low-purity lignin saccharification residue obtained after the corn straw biochemical production process is subjected to kneading-dilute alkali pretreatment and the solid and liquid two-step enzymolysis to produce sugar.
9. The fulvic acid fertilizer is characterized by being prepared by the preparation method of any one of claims 1-8.
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| CN110526766A (en) * | 2018-05-25 | 2019-12-03 | 农安县学海生物秸秆加工有限公司 | A kind of corn stover extraction fulvic acid processing organic fertilizer |
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| WO2023118073A1 (en) * | 2021-12-21 | 2023-06-29 | Luxembourg Institute Of Science And Technology | Method for the production of a humic and fulvic acid based biostimulant and fertiliser |
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| CN110526766A (en) * | 2018-05-25 | 2019-12-03 | 农安县学海生物秸秆加工有限公司 | A kind of corn stover extraction fulvic acid processing organic fertilizer |
| CN109182181A (en) * | 2018-09-14 | 2019-01-11 | 东北农业大学 | It is a kind of reduce livestock excrement composting ammonia volatilization high-temperature micro-aerobic compost keeping nitrogen bacterium and its application |
| CN112195131A (en) * | 2020-10-23 | 2021-01-08 | 张洪江 | Zymophyte liquid for preparing fulvic acid |
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