CN114365748A - Multifunctional liquid-state silico-calcium pesticide prepared from Baoqing water-containing fly ash and preparation method thereof - Google Patents
Multifunctional liquid-state silico-calcium pesticide prepared from Baoqing water-containing fly ash and preparation method thereof Download PDFInfo
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- 239000010881 fly ash Substances 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000575 pesticide Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011575 calcium Substances 0.000 title claims description 18
- 229910052791 calcium Inorganic materials 0.000 title claims description 17
- 241000894006 Bacteria Species 0.000 claims abstract description 65
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 230000001590 oxidative effect Effects 0.000 claims abstract description 31
- 239000003077 lignite Substances 0.000 claims abstract description 27
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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 claims abstract description 22
- 239000004021 humic acid Substances 0.000 claims abstract description 22
- 241000108664 Nitrobacteria Species 0.000 claims abstract description 17
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 14
- 230000005764 inhibitory process Effects 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 241000233866 Fungi Species 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- 239000006041 probiotic Substances 0.000 claims description 7
- 235000018291 probiotics Nutrition 0.000 claims description 7
- 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 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 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 claims description 6
- 239000012190 activator Substances 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 235000011010 calcium phosphates Nutrition 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000000855 fermentation Methods 0.000 claims description 6
- 230000004151 fermentation Effects 0.000 claims description 6
- 239000002509 fulvic acid Substances 0.000 claims description 6
- 229940095100 fulvic acid Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000008635 plant growth Effects 0.000 claims description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 6
- 235000011151 potassium sulphates Nutrition 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 6
- 241000228245 Aspergillus niger Species 0.000 claims description 5
- 241000223261 Trichoderma viride Species 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 241000228143 Penicillium Species 0.000 claims description 4
- 241000935922 Sphaeropsis Species 0.000 claims description 4
- 241000894120 Trichoderma atroviride Species 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 241000743698 Pinicola Species 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001546 nitrifying effect Effects 0.000 claims description 3
- 230000000529 probiotic effect Effects 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 230000008685 targeting Effects 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000012010 growth Effects 0.000 abstract description 3
- 230000007170 pathology Effects 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 description 4
- 238000003889 chemical engineering Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000207199 Citrus Species 0.000 description 3
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 description 3
- 235000020971 citrus fruits Nutrition 0.000 description 3
- 230000001066 destructive effect Effects 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 3
- 229940002612 prodrug Drugs 0.000 description 3
- 239000000651 prodrug Substances 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 244000144730 Amygdalus persica Species 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 244000070406 Malus silvestris Species 0.000 description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003415 peat Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 235000006667 Aleurites moluccana Nutrition 0.000 description 1
- 241000288953 Apina Species 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- 240000004957 Castanea mollissima Species 0.000 description 1
- 235000018244 Castanea mollissima Nutrition 0.000 description 1
- 241001481710 Cerambycidae Species 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000167847 Koelreuteria paniculata Species 0.000 description 1
- 235000005087 Malus prunifolia Nutrition 0.000 description 1
- 235000011430 Malus pumila Nutrition 0.000 description 1
- 235000015103 Malus silvestris Nutrition 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 240000003889 Piper guineense Species 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 244000294611 Punica granatum Species 0.000 description 1
- 235000014360 Punica granatum Nutrition 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- 244000305267 Quercus macrolepis Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 240000007651 Rubus glaucus Species 0.000 description 1
- 235000011034 Rubus glaucus Nutrition 0.000 description 1
- 235000009122 Rubus idaeus Nutrition 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 241001106462 Ulmus Species 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000003285 pharmacodynamic effect Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N63/00—Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
- A01N63/20—Bacteria; Substances produced thereby or obtained therefrom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
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- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Environmental Sciences (AREA)
- Microbiology (AREA)
- Virology (AREA)
- Biotechnology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
- Cultivation Of Plants (AREA)
Abstract
A multifunctional liquid-state silicon-calcium pesticide prepared from BAOQING water-containing fly ash and a preparation method thereof relate to the technical field of pesticides, and comprise nitrobacteria, hydroxide bacteria, sulfur-oxidizing bacteria, iron-manganese oxidizing bacteria and water-containing fly ash, wherein the mass ratio of the nitrobacteria to the hydroxide bacteria to the sulfur-oxidizing bacteria to the iron-manganese oxidizing bacteria is (0.001-99.999): (0.01-99.99):(0.05-99.95): (0.1-99.9). The multifunctional liquid silicon-calcium pesticide prepared from the clear water-containing fly ash and the preparation method thereof are characterized in that the inhibition rate of the multifunctional liquid silicon-calcium pesticide prepared by combining targeting functional groups of lignite humic acid according to the pathology that plants lack silicon calcium is 30-60% on the premise of promoting growth, and the multifunctional liquid silicon-calcium pesticide has significant progress and practicability.
Description
The technical field is as follows:
the invention relates to the technical field of pesticides, and particularly relates to a multifunctional liquid-state silico-calcium pesticide prepared from baoqing water-containing fly ash and a preparation method thereof.
Background art:
the citrus 'yellow shoot disease' is also called 'yellow shoot disease' and 'yellow blight', belongs to a pest for national quarantine, is a destructive disease with the most serious harm and the most destructive harm in citrus production, and is called as citrus 'cancer'. The pink-neck longicorn is an important trunk-boring pest of a plurality of fruit trees, forest trees and ornamental trees. Because the damage is hidden, the prevention and the treatment are difficult, and destructive disasters are often caused. The host plants include peach, apricot, plum, cherry, apple, crabapple, goldenrain tree, willow, poplar, elm, mulberry, persimmon, pomegranate, Chinese chestnut, oak, raspberry and pepper, and the rose trees and ornamental plants are mainly used, wherein the damage of the peach trees is the most serious.
Silicon has many uses, and natural silicon resources are also in a compound state, and the patent application number is 201911366996.7; 202010275496.9, national energy investment group Limited company discloses a way to change free silicon and liquid silicon into valuable from 'a method for preparing alkali-free silicon fertilizer from acid treatment liquid containing silicon and alkali-free silicon fertilizer' and 'liquid calcium silicon fertilizer and a preparation method and application thereof'; a method for preparing a targeting prodrug from peat, the targeting prodrug and application thereof, namely Yunyun combined pharmaceutical industry, namely, the Limited liability company, China eastern science and technology university, with an authorization publication number CN201310738174, and a method for preparing a medical prodrug by extracting bioactive substances from peat humic acid and coordinating the bioactive substances with a molecular imprinting method; although not completely in a technical field, the Shanghai fine derivative science and technology granted patent ZL201710547454.4, a method for preparing a composite culture medium and a symbiotic inclusion compound of arbuscular mycorrhizal fungi and a multifunctional liquid silico-calcium pesticide prepared from fly ash are expected to reduce the application amount of chemical pesticides and increase the effectiveness of ecological prevention and treatment by introducing and modifying key pharmacophores.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provide a multifunctional liquid calcium silicon pesticide prepared from Baoqing water-containing fly ash and a preparation method thereof.
In order to solve the problems existing in the background technology, the invention adopts the following technical scheme: comprises nitrobacteria, hydroxide bacteria, sulfur-oxidizing bacteria, iron-manganese oxidizing bacteria and water-containing fly ash, wherein the mass ratio of the nitrobacteria to the hydroxide bacteria to the iron-manganese oxidizing bacteria is (0.001-99.999): (0.01-99.99):(0.05-99.95): (0.1-99.9).
The nitrobacteria, the hydroxide bacteria, the sulfur oxidizing bacteria and the iron manganese oxidizing bacteria are activated by adopting lignite humic acid, lignite fulvic acid, calcium phosphate, potassium sulfate, ammonium bicarbonate and sodium chloride as activators, wherein the mass ratio of the activating concentration of the lignite humic acid, the lignite fulvic acid, the calcium phosphate, the potassium sulfate, the ammonium bicarbonate and the sodium chloride to the activating concentration of the bacteria is (0.1-99.9), (1-99), (10-90), the activating temperature is-30-75 ℃, and the activating time is 12-96 hours.
The mass ratio of the fly ash to the water in the water-containing fly ash is 5.0-95.0.
The fermentation temperature of the nitrobacteria, the hydroxide bacteria, the sulfur oxidizing bacteria, the iron manganese oxidizing bacteria, the activator and the water-containing fly ash is 50-75 ℃.
The mass concentration of the silicon, magnesium, calcium and iron hydrolyzed into silicic acid in the hydrous fly ash is 5.00-20.00%.
The lignite humic acid contains a pharmacophore structure of-COOH, -OH, -CHO, -O-, -OCH3, and the pharmacophore structure is increased by 3 times after extraction and enrichment.
The preparation steps are as follows:
1) mixing activated and preserved nitrifying bacteria, hydrogen oxidizing bacteria, sulfur oxidizing bacteria and iron manganese oxidizing bacteria with the water-containing fly ash according to the mass ratio of (0.001-99.999): (0.01-99.99):(0.05-99.95): (0.1-99.9) high-temperature fermentation;
2) hydrolyzing, phase-change enriching to obtain liquid silicon-containing substance, and preparing into multifunctional liquid silicon-calcium composite pesticide under the action of exogenous in-forest fungi and lignite humic acid.
The selected fungus in forest is two or three of Sphaeropsis pinicola, Trichoderma viride, Penicillium sp, Aspergillus niger and Trichoderma atroviride, and is domesticated in liquid silicon with the concentration of 1-5% at 10-35 deg.C for 36-72 h.
The prepared multifunctional liquid calcium silicon pesticide has the technical indexes that: 5.0 to 50 percent of silicon, 6.0 to 7.0 pH value, 50/g of probiotic content, 10.0 to 25.0 percent of yield increase and plant growth promotion, and 30 to 70 percent of harmful germ inhibition rate.
The multifunctional liquid silicon calcium pesticide has the beneficial effects that the inhibition rate of the multifunctional liquid silicon calcium pesticide prepared by combining the targeting functional groups of lignite humic acid according to the pathology of lacking silicon calcium of plants is 30-60% on the premise of promoting growth, and the multifunctional liquid silicon calcium pesticide has significant progress and practicability.
Description of the drawings:
FIG. 1 is an Infrared (IR) spectrum of lignite before humic acid pharmacophore enrichment according to the present invention;
FIG. 2 is an infrared spectrum (IR) diagram of lignite humic acid pharmacophore enriched.
The specific implementation mode is as follows:
the invention specifically adopts the following implementation modes: comprises nitrobacteria, hydroxide bacteria, sulfur oxidizing bacteria, iron manganese oxidizing bacteria and water-containing fly ash, wherein the mass ratio of the nitrobacteria to the hydroxide bacteria to the sulfur oxidizing bacteria to the iron manganese oxidizing bacteria is (0.001-99.999): (0.01-99.99):(0.05-99.95): (0.1-99.9). The nitrobacteria, the hydroxide bacteria, the sulfur oxidizing bacteria and the iron manganese oxidizing bacteria are activated by adopting lignite humic acid, lignite fulvic acid, calcium phosphate, potassium sulfate, ammonium bicarbonate and sodium chloride as activators, wherein the mass ratio of the activating concentration of the lignite humic acid, the lignite fulvic acid, the calcium phosphate, the potassium sulfate, the ammonium bicarbonate and the sodium chloride to the activating concentration of the bacteria is (0.1-99.9), (1-99), (10-90), the activating temperature is-30-75 ℃, and the activating time is 12-96 hours. The mass ratio of the fly ash to the water in the water-containing fly ash is 5.0-95.0. The fermentation temperature of the nitrobacteria, the hydroxide bacteria, the sulfur oxidizing bacteria, the iron manganese oxidizing bacteria, the activator and the water-containing fly ash is 50-75 ℃. The mass concentration of the silicon, magnesium, calcium and iron hydrolyzed into silicic acid in the hydrous fly ash is 5.00-20.00%. The lignite humic acid contains a pharmacophore structure of-COOH, -OH, -CHO, -O-, -OCH3, and the pharmacophore structure is increased by 3 times after extraction and enrichment.
The preparation steps are as follows:
1) mixing activated and preserved nitrifying bacteria, hydrogen oxidizing bacteria, sulfur oxidizing bacteria and iron manganese oxidizing bacteria with the water-containing fly ash according to the mass ratio of (0.001-99.999): (0.01-99.99):(0.05-99.95): (0.1-99.9) high-temperature fermentation;
2) hydrolyzing, phase-change enriching to obtain liquid silicon-containing substance, and preparing into multifunctional liquid silicon-calcium composite pesticide under the action of exogenous in-forest fungi and lignite humic acid.
The selected fungus in forest is two or three of Sphaeropsis pinicola, Trichoderma viride, Penicillium sp, Aspergillus niger and Trichoderma atroviride, and is domesticated in liquid silicon with the concentration of 1-5% at 10-35 deg.C for 36-72 h. The prepared multifunctional liquid calcium silicon pesticide has the technical indexes that: 5.0 to 50 percent of silicon, 6.0 to 7.0 pH, 50/g of probiotic content, 10.0 to 25.0 percent of yield increase and plant growth promotion, and 30 to 70 percent of harmful germ inhibition rate.
The mass ratio of the fly ash to the water in the hydrous fly ash is 5.0: 95.0, under the action of the microbial bacteria, the silicide in the fermented fly ash is hydrolyzed into silicic acid:
MgFeSiO4+CO2+H2OMg 2++HCO3+H4SIO4+Fe2++OH-
MgCaFeSiO4+CO2+H2OMg 2++Ca+HCO3+H4SIO4+Fe2++OH-
the magnesium, calcium and iron silicate in the hydrous fly ash is hydrolyzed into silicic acid with the mass concentration of 5.00-15.00%.
The Baoqing lignite humic acid contains pharmacophore structures such as-COOH, R-OH, -CHO, -O-, -OCH3 and the like, and infrared spectroscopic analysis and determination carried out on a national test platform of chemical engineering 985 of China university of eastern science and technology show that the pharmacophore is increased by more than 3 times after extraction and enrichment (see the attached drawing of the specification)
Any one of the prepared multifunctional liquid calcium silicon pesticide has the technical indexes that: 5.0 to 50 percent of silicon, 6.0 to 7.0 pH and 0.2 hundred million/g of probiotics CFU, 10.0 to 25.0 percent of yield increase and plant growth promotion, and 30 to 60 percent of harmful germ inhibition rate.
Example one
Activated nitrobacteria, hydrogen hydroxide bacteria, sulfur oxide bacteria, iron manganese oxide bacteria and fly ash containing 90% of water are fermented at 70 ℃ according to the mass ratio of 0.01-99.99, hydrolysis is carried out to obtain the free silicic acid with the mass concentration of 10.00%, and the free silicic acid is domesticated in Baoqing humic acid solution containing-COOH, R-OH, -CHO, -O-, -OCH3 and other pharmacopoeia structures of the fungus, namely, Sphaeropsis apina, Trichoderma viride and Aspergillus belonging to 35 ℃ and liquid silicon with the concentration of 5% and lignite provided by research center of Zhejiang academy of agricultural sciences, wherein the pharmacopoeia is increased by 3 times after being extracted by infrared spectroscopy (shown in attached drawing) through analysis and determination of a national test platform of chemical engineering 985 of Huadong university; the prepared multifunctional liquid calcium silicon pesticide has the technical indexes that: 10.0 percent of silicon, 6.0 pH and 0.2 hundred million probiotics CFU/g.
Example two
Activated nitrobacteria, hydrogen hydroxide bacteria, sulfur oxide bacteria, iron manganese oxide bacteria and fly ash containing 90% of water are fermented at 70 ℃ according to the mass ratio of 0.01-99.99, hydrolysis is carried out to obtain the free silicic acid with the mass concentration of 10.00%, the free silicic acid is domesticated for 36-72h in a forest fungus Trichoderma viride, Aspergillus niger and Trichoderma atroviride liquid with the concentration of 5% provided by research center of Zhejiang academy of agricultural sciences, and a Baoqing lignite humic acid solution containing pharmacodynamic structures of-COOH, R-OH, -CHO, -O-, -OCH3 and the like, and infrared spectroscopic analysis and determination carried out by a national test platform of chemical engineering 985 of eastern China university shows that the pharmacophore is increased by 3 times after extraction and enrichment (see attached drawing); the prepared multifunctional liquid calcium silicon pesticide has the technical indexes that: 10.0 percent of silicon, 6.0 pH and 0.2 hundred million/g of probiotics CFU, the yield is increased, the plant growth is promoted by 10.0 percent, and the inhibition rate of harmful germs is 30 percent.
EXAMPLE III
Activated nitrobacteria, hydrogen hydroxide bacteria, sulfur oxide bacteria, iron manganese oxide bacteria and fly ash containing 90% of water are fermented at 70 ℃ according to the mass ratio of 0.01-99.99, hydrolysis is carried out to obtain the free silicic acid with the mass concentration of 10.00%, the free silicic acid is domesticated for 36-72h in a Baoqing lignite humic acid solution containing a pharmacophore structure of-COOH, R-OH, -CHO, -O-, -OCH3 and the like, wherein the concentration of the free silicic acid is 35 ℃ compared with that of the forest fungi Sphaeropisissaapeea, Penicillium and Aspergillus niger, which are provided by research center of Zhejiang academy of agriculture, and the infrared spectroscopic analysis and measurement carried out by a national test platform of chemical engineering 985 of Huadong university shows that the pharmacophore structure is increased by 3 times after extraction and enrichment (see attached drawing); the prepared multifunctional liquid calcium silicon pesticide has the technical indexes that: 10.0 percent of silicon, 6.0 pH and 0.2 hundred million/g of probiotics CFU, 25.0 percent of yield increase and plant growth promotion, and 60 percent of harmful germ inhibition rate.
In conclusion, the multifunctional liquid silicon-calcium pesticide prepared from the Baqing water-containing fly ash and the preparation method thereof have the advantages that the inhibition rate of the multifunctional liquid silicon-calcium pesticide prepared by combining the targeting functional groups of lignite humic acid according to the pathology that plants lack silicon calcium is 30-60% on the premise of promoting growth, and the preparation method has significant progress and practicability.
Claims (9)
1. A multifunctional liquid-state silico-calcium pesticide prepared from Baoqing water-containing fly ash is characterized in that: comprises nitrobacteria, hydroxide bacteria, sulfur-oxidizing bacteria, iron-manganese oxidizing bacteria and water-containing fly ash, wherein the mass ratio of the nitrobacteria to the hydroxide bacteria to the iron-manganese oxidizing bacteria is (0.001-99.999): (0.01-99.99):(0.05-99.95): (0.1-99.9).
2. The multifunctional liquid silico-calcium pesticide prepared from the Baqing water-containing fly ash according to claim 1, which is characterized in that: the nitrobacteria, the hydroxide bacteria, the sulfur oxidizing bacteria and the iron manganese oxidizing bacteria are activated by adopting lignite humic acid, lignite fulvic acid, calcium phosphate, potassium sulfate, ammonium bicarbonate and sodium chloride as activators, wherein the mass ratio of the activating concentration of the lignite humic acid, the lignite fulvic acid, the calcium phosphate, the potassium sulfate, the ammonium bicarbonate and the sodium chloride to the activating concentration of the bacteria is (0.1-99.9), (1-99), (10-90), the activating temperature is-30-75 ℃, and the activating time is 12-96 hours.
3. The multifunctional liquid silico-calcium pesticide prepared from the Baqing water-containing fly ash according to claim 1, which is characterized in that: the mass ratio of the fly ash to the water in the water-containing fly ash is 5.0-95.0.
4. The multifunctional liquid silico-calcium pesticide prepared from the Baoqing water-containing fly ash according to claim 1 or 2, which is characterized in that: the fermentation temperature of the nitrobacteria, the hydroxide bacteria, the sulfur oxidizing bacteria, the iron manganese oxidizing bacteria, the activator and the water-containing fly ash is 50-75 ℃.
5. The multifunctional liquid silico-calcium pesticide prepared from the Baqing water-containing fly ash according to claim 1, which is characterized in that: the mass concentration of the silicon, magnesium, calcium and iron hydrolyzed into silicic acid in the hydrous fly ash is 5.00-20.00%.
6. The multifunctional liquid silico-calcium pesticide prepared from the Baqing water-containing fly ash according to claim 2, which is characterized in that: lignite humic acid contains a pharmacophore structure of-COOH, -OH, -CHO, -O-, -OCH3, and the pharmacophore structure is increased by 3 times after extraction and enrichment.
7. The preparation method of the multifunctional liquid silico-calcium pesticide prepared from the Baoqing water-containing fly ash according to claim 1 is characterized by comprising the following steps: the method comprises the following steps:
1) mixing activated and preserved nitrifying bacteria, hydrogen oxidizing bacteria, sulfur oxidizing bacteria and iron manganese oxidizing bacteria with the water-containing fly ash according to the mass ratio of (0.001-99.999): (0.01-99.99):(0.05-99.95): (0.1-99.9) high-temperature fermentation;
2) hydrolyzing, phase-change enriching to obtain liquid silicon-containing substance, and preparing into multifunctional liquid silicon-calcium composite pesticide under the action of exogenous in-forest fungi and lignite humic acid.
8. The multifunctional liquid silico-calcium pesticide prepared from the Baqing water-containing fly ash according to claim 7, which is characterized in that: the selected fungus in forest is two or three of Sphaeropsis pinicola, Trichoderma viride, Penicillium sp, Aspergillus niger and Trichoderma atroviride, and is domesticated in liquid silicon with the concentration of 1-5% at 10-35 deg.C for 36-72 h.
9. The multifunctional liquid silico-calcium pesticide prepared from the Baoqing water-containing fly ash according to claim 1 or 7, which is characterized in that: the prepared multifunctional liquid calcium silicon pesticide has the technical indexes that: 5.0 to 50 percent of silicon, 6.0 to 7.0 pH value, 50/g of probiotic content, 10.0 to 25.0 percent of yield increase and plant growth promotion, and 30 to 70 percent of harmful germ inhibition rate.
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| 杨展览，李希圣，黄伟雄: "《地理学大辞典》", 30 September 1992, 安徽人民出版社 * |
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