CN117024220B - Mixed pesticide fertilizer for soil remediation and preparation method thereof - Google Patents
Mixed pesticide fertilizer for soil remediation and preparation method thereof Download PDFInfo
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- CN117024220B CN117024220B CN202311022242.6A CN202311022242A CN117024220B CN 117024220 B CN117024220 B CN 117024220B CN 202311022242 A CN202311022242 A CN 202311022242A CN 117024220 B CN117024220 B CN 117024220B
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- humic acid
- fertilizer
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- 239000002689 soil Substances 0.000 title claims abstract description 107
- 239000003337 fertilizer Substances 0.000 title claims abstract description 43
- 239000000575 pesticide Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005067 remediation Methods 0.000 title claims description 21
- 239000002131 composite material Substances 0.000 claims abstract description 54
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical class C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003463 adsorbent Substances 0.000 claims abstract description 30
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 27
- 229920001661 Chitosan Polymers 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 239000003895 organic fertilizer Substances 0.000 claims abstract description 9
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010902 straw Substances 0.000 claims description 43
- 239000004021 humic acid Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 241000196324 Embryophyta Species 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- -1 nitro humic acid Chemical compound 0.000 claims description 15
- 229960000583 acetic acid Drugs 0.000 claims description 14
- 239000012362 glacial acetic acid Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 9
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 9
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 9
- 239000011425 bamboo Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001723 curing Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000000605 extraction Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 9
- 241001330002 Bambuseae Species 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 230000008439 repair process Effects 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 230000026731 phosphorylation Effects 0.000 description 5
- 238000006366 phosphorylation reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 240000008436 Ipomoea aquatica Species 0.000 description 3
- 235000019004 Ipomoea aquatica Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000035558 fertility Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 231100000674 Phytotoxicity Toxicity 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000123326 Fomes Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- ZIXVIWRPMFITIT-UHFFFAOYSA-N cadmium lead Chemical compound [Cd].[Pb] ZIXVIWRPMFITIT-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000005527 soil sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- 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
- C05G3/70—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting wettability, e.g. drying agents
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Soil Sciences (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a soil restoration mixed pesticide fertilizer and a preparation method thereof, belonging to the technical field of soil restoration, wherein the soil restoration mixed pesticide fertilizer comprises the following components in parts by weight: 30-50 parts of a composite adsorbent, 15-20 parts of an organic fertilizer, 10-15 parts of turfy soil, 6-10 parts of urea, 15-25 parts of calcium borate, 8-12 parts of chitosan, 10-15 parts of organic acid and 1-5 parts of a water-retaining agent, wherein the composite adsorbent is polypyrrole/porous biochar loaded phosphorylated humic acid. The invention provides a soil restoration mixed pesticide fertilizer and a preparation method thereof, and aims to solve the problem of poor restoration effect of soil heavy metal combined pollution.
Description
Technical Field
The invention belongs to the technical field of soil remediation, and particularly relates to a soil remediation mixed pesticide fertilizer and a preparation method thereof.
Background
Soil heavy metal pollution is an environmental problem which is serious in recent years, and not only changes the property of the soil and inhibits the growth and photosynthesis of plants, but also can migrate into the bodies of people and animals through food chains, so that serious health problems are caused; in the aspect of soil pollution treatment technology, the in-situ passivation method is widely applied to the soil for treating heavy metal pollution due to simple operation, low cost and good effect, however, in-situ passivation has substrate selectivity, in actual polluted soil, the combined pollution is quite common, such as cadmium-lead combined pollution, therefore, the biological effectiveness of various heavy metal ions is difficult to reduce simultaneously by a single repair technology, the efficiency is low, the repair is incomplete, the heavy metal pollution concentration of the soil is high, the plant growth is slow, the repair period is long, the practical engineering is greatly limited, and the repair effect of the prior repair technology is difficult to reach expectations.
The prior art mainly has the following problems: the restoration effect of the soil heavy metal composite pollution is poor, and even secondary pollution is caused.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides the soil restoration mixed pesticide fertilizer and the preparation method thereof, and in order to solve the problems of poor restoration effect and even secondary pollution caused by the heavy metal composite pollution of soil, the invention provides the preparation method of the soil restoration mixed pesticide fertilizer, which selects plant straws as a biochar raw material, and obtains the polypyrrole/porous biochar composite material by firstly activating biomass and then modifying polypyrrole, thereby ensuring that the composite material not only has a large specific surface and rich pore channel structures, but also can realize the efficient adsorption of metal anions, and simultaneously carries out phosphorylation modification on humic acid, and the humic acid modified by the phosphorylation is loaded on the polypyrrole/porous biochar composite material, so that the passivation efficiency of metal cations is improved, the soil functions and fertility are effectively improved, and the phytotoxicity is reduced.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a soil restoration mixed pesticide fertilizer which comprises the following components in parts by weight: 30-50 parts of composite adsorbent, 15-20 parts of organic fertilizer, 10-15 parts of turfy soil, 6-10 parts of urea, 15-25 parts of calcium borate, 8-12 parts of chitosan, 10-15 parts of organic acid and 1-5 parts of water-retaining agent; the composite adsorbent is polypyrrole/porous biochar composite material loaded phosphorylated humic acid.
Preferably, the preparation method of the composite adsorbent specifically comprises the following steps:
S1, removing impurities from plant straws, cleaning, drying, grinding, and screening with a 60-mesh sieve to obtain plant straw powder;
S2, taking plant straw powder, soaking the plant straw powder in 20% phosphoric acid for 18-20 hours, drying the plant straw powder at 80 ℃ for 24-26 hours, putting the plant straw powder into a muffle furnace which is filled with N 2 for pyrolysis for 2-3 hours, setting the pyrolysis temperature to 500 ℃, cooling the plant straw powder, taking out a sample, washing the sample to be neutral, drying the sample at 80 ℃ for 10-12 hours, and grinding the sample to obtain activated biochar;
S3, dispersing the activated biochar prepared in the S2 in 2% glacial acetic acid solution, adding pyrrole monomer and 1mol/LFeCl 3, stirring for 3-5h, refrigerating in a refrigerator for 12-15h, regulating pH to 5.8, centrifuging at 4000r/min for 8-10min, collecting precipitate, washing, and freeze-drying to obtain polypyrrole/porous biochar composite material;
s4, adding 8moL/L nitric acid solution into humic acid, uniformly stirring, sealing and curing, washing with deionized water until the pH is 7, and naturally airing to obtain nitro humic acid;
S5, dissolving nitro humic acid in distilled water, heating to 70-75 ℃ under stirring, adding NH 4H2PO4 for reaction for 60min, cooling to room temperature, and drying at 50 ℃ for 24h to obtain modified humic acid;
s6, dissolving the modified humic acid in distilled water, adding the polypyrrole/porous biochar composite material prepared in the step S3, magnetically stirring at 180rpm for 48h, standing for 24h, washing with distilled water until the pH is 7, and freeze-drying for 24h to obtain the composite adsorbent.
Preferably, in S1, the plant straw is one or more of rape straw, cotton straw, corn straw, bamboo straw, rice hull straw;
Preferably, in S1, the feed liquid ratio of the plant straw powder to the phosphoric acid is 1:10-12;
preferably, in S3, the feed liquid ratio of the activated biochar to the 2% glacial acetic acid solution is 1:100-150;
Preferably, in S3, the addition amount of the pyrrole monomer is 0.3% -0.4% of 2% glacial acetic acid solution;
Preferably, in S3, the molar ratio of pyrrole monomer to 1mol/LFeCl 3 is 2.5:1;
Preferably, in S4, the mass ratio of the humic acid to the nitric acid solution is 1:15-20;
preferably, in S5, the mass fraction of the nitro humic acid in distilled water is 5% -6%;
Preferably, in S5, the mass ratio of the nitro humic acid to the NH 4H2PO4 is 1.5-2:1;
preferably, in S6, the mass fraction of the modified humic acid in distilled water is 4% -5%;
preferably, in S6, the mass ratio of the modified humic acid to the polypyrrole/porous biochar composite material is 1:5-6.
The invention also provides a preparation method of the soil restoration mixed pesticide fertilizer, which specifically comprises the following steps:
(1) Mixing the organic fertilizer, urea and calcium borate, sequentially adding turfy soil, organic acid and chitosan, and continuously stirring and mixing to obtain a first mixture;
(2) And adding the composite adsorbent and the water-retaining agent into the first mixture, and uniformly stirring to obtain the soil remediation mixed pesticide fertilizer.
The beneficial effects obtained by the invention are as follows:
according to the invention, plant straws are selected as biochar raw materials, and polypyrrole is used for compounding to obtain the polypyrrole/porous biochar composite material by activating biomass firstly, so that the composite material is ensured to contain a large specific surface and rich pore channel structures, and can realize efficient adsorption of metal anions, and simultaneously, humic acid is subjected to phosphorylation modification and is loaded on the polypyrrole/porous biochar composite material, so that the passivation efficiency of metal cations is improved, the soil function and fertility are effectively improved, and the phytotoxicity is reduced; the activated biochar has a richer pore canal structure, the adsorption speed and the adsorption capacity of heavy metal elements are increased, the chemical stability is good, however, the adsorption capacity of some metal elements such as cadmium is irrelevant to the pore structure change of the biochar, cr (VI) is mostly in the form of anionic groups Cr 2O7 2-、HCrO4- and the like in the environment, the toxicity is high, the activated biochar is not easy to adsorb, and the polypyrrole has the advantages of good conductivity, easy polymerization, good biocompatibility, good ion exchange performance, low cost, environmental friendliness and the like, and under the acidic condition, the N + with positive charges is generated by the deprotonation of amino groups on the polypyrrole, and the activated biochar is compounded with the capability of adsorbing the anionic groups through electrostatic attraction, so that the efficient adsorption of metal anions is realized; the humic acid has the advantages that functional groups such as hydroxyl and carboxyl contained in the humic acid molecules can perform adsorption precipitation, ion exchange, complexation and the like with heavy metal cations, the humic acid-heavy metal complex after the complexation is positively charged, the soil particle colloid is negatively charged, so that electrostatic adsorption can occur between the humic acid and the heavy metal complex, the adsorption rate of heavy metal on soil is accelerated, however, the humic acid has weak capability of combining heavy metals, the application of the humic acid is limited, the humic acid is subjected to phosphorylation modification, the slight corrosion effect of NH 4H2PO4 on the humic acid is utilized, the specific surface area is increased, the passivation capability of the heavy metal cations is improved, in addition, the salt content of the soil is increased due to the fact that soluble alkali ions (such as Ca 2+、K+ and the like) in the biochar are combined with Ca 2+、K+ plasma to generate soluble humic acid, the soil can be improved, and the soil fertility is improved.
Drawings
FIG. 1 is a graph showing the results of the ratios of the different forms of heavy metal Cu in soil after the application of the soil restoration medical fertilizer prepared in the examples and the comparative examples;
FIG. 2 is a graph showing the results of the ratios of the different forms of heavy metal Cd in soil after the application of the soil restoration pesticide fertilizer prepared in the examples and the comparative examples;
FIG. 3 is a graph showing the results of the ratio of the different forms of Pb in soil after application of the soil remediation chemical fertilizer prepared in the examples and comparative examples of the present invention;
FIG. 4 is a graph showing the results of the ratios of the different forms of heavy metal Cr in soil after the application of the soil restoration medical fertilizer prepared in the examples and the comparative examples of the invention;
FIG. 5 is a graph showing the results of the content of heavy metal TCLP-Cu in soil after application of the soil remediation medical fertilizer prepared in the examples and the comparative examples of the present invention;
FIG. 6 is a graph showing the content result of the heavy metal TCLP-Cd in soil after application of the soil remediation medical fertilizer prepared in the examples and the comparative examples of the invention;
FIG. 7 is a graph showing the results of the content of heavy metal TCLP-Pb in soil after application of the soil remediation medical fertilizer prepared in the examples and comparative examples of the present invention;
FIG. 8 is a graph showing the results of the content of heavy metal TCLP-Cr in soil after application of the soil remediation medical fertilizer prepared in the examples and comparative examples of the present invention;
fig. 9 is an SEM image of the composite adsorbent prepared in example 1 of the present invention.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials and test strains used in the examples described below, unless otherwise specified, were commercially available.
Sodium hydroxide, phosphoric acid, nitric acid, absolute ethanol are all purchased from national pharmaceutical group chemical reagent company, inc; pyrrole was purchased from Shanghai Ala Biochemical technologies Co., ltd; iron trichloride was purchased from fomes (Tianjin) chemical reagent limited; glacial acetic acid was purchased from the Tianjin Dongtianzheng fine chemical reagent factory; humic acid was purchased from the company Miou chemical Co., ltd; monoammonium phosphate (NH 4H2PO4) was purchased from shanghai source leaf biotechnology limited.
Example 1
The invention provides a soil restoration mixed pesticide fertilizer which comprises the following components in parts by weight: 30 parts of a composite adsorbent, 15 parts of an organic fertilizer, 10 parts of turfy soil, 6 parts of urea, 15 parts of calcium borate, 8 parts of chitosan, 10 parts of an organic acid and 1 part of a water-retaining agent; the composite adsorbent is polypyrrole/porous biochar composite material loaded phosphorylated humic acid.
The preparation method of the composite adsorbent specifically comprises the following steps:
s1, removing impurities from rape straw, cleaning, drying, grinding, and screening with a 60-mesh sieve to obtain rape straw powder;
S2, taking rape straw powder, adding 20% phosphoric acid according to a feed-liquid ratio of 1:10, soaking for 18 hours, placing in a 80 ℃ constant-temperature blast drying oven for drying for 24 hours, placing in a muffle furnace which is filled with N 2, pyrolyzing for 2 hours at a set temperature of 500 ℃ at a heating rate of 10 ℃/min, cooling, taking out a sample, repeatedly washing to be neutral by using ultrapure water, drying in an 80 ℃ oven for 10 hours, and grinding to obtain activated biochar;
S3, taking activated biochar prepared in the step S2, adding 2% glacial acetic acid solution according to a feed liquid ratio of 1:100, uniformly stirring, adding pyrrole monomer according to the addition amount of 0.3% of the 2% glacial acetic acid solution, uniformly mixing, adding 1mol/LFeCl 3 according to a molar ratio of 2.5:1 with the pyrrole monomer, stirring for reacting for 3 hours, placing in a refrigerator for refrigerating for 12 hours, adjusting pH to 5.8, centrifuging for 8 minutes at 4000r/min, taking precipitate, washing the precipitate with deionized water and absolute ethyl alcohol until filtrate is neutral, and freeze-drying for 36 hours under the conditions of-50 ℃ and 20pa to obtain polypyrrole/porous biochar composite material;
S4, taking humic acid, adding 8moL/L nitric acid solution according to the mass ratio of 1:15, uniformly stirring, sealing and curing, washing with deionized water until the pH value is 7, and naturally airing to obtain nitro humic acid;
S5, dissolving the nitro humic acid prepared in the S4 into distilled water according to the mass fraction of 5%, heating to 70 ℃ while stirring, adding NH 4H2PO4 according to the mass ratio of 1.5:1, reacting for 60min, cooling to room temperature, and drying at 50 ℃ for 24h to obtain modified humic acid;
S6, taking the modified humic acid prepared in the step S5, dissolving the modified humic acid in distilled water according to the mass fraction of 4%, adding the polypyrrole/porous biochar composite material prepared in the step S3 according to the mass ratio of 1:5, magnetically stirring at 180rpm for 48h, standing for 24h, washing with distilled water until the pH is 7, and freeze-drying for 24h to obtain the composite adsorbent.
The invention also provides a preparation method of the soil restoration mixed pesticide fertilizer, which specifically comprises the following steps:
(1) Mixing the organic fertilizer, urea and calcium borate, sequentially adding turfy soil, organic acid and chitosan, and continuously stirring for 0.5h to obtain a first mixture;
(2) And adding the composite adsorbent and the water-retaining agent into the first mixture, and uniformly stirring to obtain the soil remediation mixed pesticide fertilizer.
Example 2
The invention provides a soil restoration mixed pesticide fertilizer which comprises the following components in parts by weight: 40 parts of a composite adsorbent, 17 parts of an organic fertilizer, 13 parts of turfy soil, 8 parts of urea, 18 parts of calcium borate, 10 parts of chitosan, 12 parts of an organic acid and 3 parts of a water-retaining agent; the composite adsorbent is polypyrrole/porous biochar composite material loaded phosphorylated humic acid.
The preparation method of the composite adsorbent specifically comprises the following steps:
S1, removing impurities from bamboo straw, cleaning, drying, grinding, and screening with a 60-mesh sieve to obtain bamboo straw powder;
S2, taking bamboo straw powder, adding 20% phosphoric acid according to a feed-liquid ratio of 1:11 for soaking for 19 hours, placing the bamboo straw powder in an 80 ℃ constant-temperature blast drying oven for drying for 25 hours, placing the bamboo straw powder in a muffle furnace filled with N 2, pyrolyzing the bamboo straw powder at a set temperature of 500 ℃ for 2.5 hours at a heating rate of 10 ℃/min, cooling the bamboo straw powder, taking out a sample, repeatedly washing the sample with ultrapure water to be neutral, drying the sample in an 80 ℃ oven for 11 hours, and grinding the sample to obtain activated biochar;
S3, taking activated biochar prepared in the step S2, adding 2% glacial acetic acid solution according to a feed liquid ratio of 1:120, uniformly stirring, adding pyrrole monomer according to the addition amount of 0.3% of the 2% glacial acetic acid solution, uniformly mixing, adding 1mol/LFeCl 3 according to a molar ratio of 2.7:1 with the pyrrole monomer, stirring for reacting for 3 hours, placing in a refrigerator for refrigerating for 14 hours, adjusting pH to 5.8, centrifuging for 9 minutes at 4000r/min, taking precipitate, washing the precipitate with deionized water and absolute ethyl alcohol until filtrate is neutral, and freeze-drying for 36 hours under the conditions of-50 ℃ and 20pa to obtain polypyrrole/porous biochar composite material;
s4, taking humic acid, adding 8moL/L nitric acid solution according to the mass ratio of 1:18, uniformly stirring, sealing and curing, washing with deionized water until the pH value is 7, and naturally airing to obtain nitro humic acid;
S5, dissolving the nitro humic acid prepared in the S4 into distilled water according to the mass fraction of 5%, heating to 70 ℃ while stirring, adding NH 4H2PO4 according to the mass ratio of 1.7:1, reacting for 60min, cooling to room temperature, and drying at 50 ℃ for 24h to obtain the modified humic acid;
S6, taking the modified humic acid prepared in the step S5, dissolving the modified humic acid in distilled water according to the mass fraction of 4%, adding the polypyrrole/porous biochar composite material prepared in the step S3 according to the mass ratio of 1:5.5, magnetically stirring at 180rpm for 48h, standing for 24h, washing with distilled water until the pH is 7, and freeze-drying for 24h to obtain the composite adsorbent.
In addition, the invention also provides a preparation method of the soil restoration mixed pesticide fertilizer, and the preparation method is implemented according to the embodiment 1.
Example 3
The invention provides a soil restoration mixed pesticide fertilizer which comprises the following components in parts by weight: 50 parts of a composite adsorbent, 20 parts of an organic fertilizer, 15 parts of turfy soil, 10 parts of urea, 25 parts of calcium borate, 12 parts of chitosan, 15 parts of an organic acid and 5 parts of a water-retaining agent; the composite adsorbent is polypyrrole/porous biochar composite material loaded phosphorylated humic acid.
The preparation method of the composite adsorbent specifically comprises the following steps:
s1, removing impurities from cotton straw, cleaning, drying, grinding, and screening with a 60-mesh sieve to obtain cotton straw powder;
s2, taking cotton straw powder, adding 20% phosphoric acid according to a feed-liquid ratio of 1:12, soaking for 20 hours, placing in a 80 ℃ constant-temperature blast drying oven for drying for 26 hours, placing in a muffle furnace which is filled with N 2, pyrolyzing for 3 hours at a set temperature of 500 ℃ at a heating rate of 10 ℃/min, cooling, taking out a sample, repeatedly washing to be neutral by using ultrapure water, drying in an 80 ℃ oven for 12 hours, and grinding to obtain activated biochar;
s3, taking activated biochar prepared in the step S2, adding 2% glacial acetic acid solution according to a feed liquid ratio of 1:150, uniformly stirring, adding pyrrole monomer according to an addition amount of 0.4% of the 2% glacial acetic acid solution, uniformly mixing, adding 1mol/LFeCl 3 according to a molar ratio of 2.5:1 with the pyrrole monomer, stirring for reacting for 5 hours, placing in a refrigerator for refrigerating for 15 hours, regulating pH to 5.8, centrifuging for 10 minutes at 4000r/min, taking precipitate, washing the precipitate with deionized water and absolute ethyl alcohol until filtrate is neutral, and freeze-drying for 36 hours at-50 ℃ under the condition of 20pa to obtain the polypyrrole/porous biochar composite material;
S4, taking humic acid, adding 8moL/L nitric acid solution according to the mass ratio of 1:20, uniformly stirring, sealing and curing, washing with deionized water until the pH value is 7, and naturally airing to obtain nitro humic acid;
S5, dissolving the nitro humic acid prepared in the step S4 into distilled water according to the mass fraction of 6%, heating to 75 ℃ while stirring, adding NH 4H2PO4 according to the mass ratio of 2:1, reacting for 60min, cooling to room temperature, and drying at 50 ℃ for 24h to obtain modified humic acid;
S6, taking the modified humic acid prepared in the step S5, dissolving the modified humic acid in distilled water according to the mass fraction of 5%, adding the polypyrrole/porous biochar composite material prepared in the step S3 according to the mass ratio of 1:6, magnetically stirring at 180rpm for 48h, standing for 24h, washing with distilled water until the pH is 7, and freeze-drying for 24h to obtain the composite adsorbent.
In addition, the invention also provides a preparation method of the soil restoration mixed pesticide fertilizer, and the preparation method is implemented according to the embodiment 1.
Comparative example 1
This comparative example provides a soil restoration compound fertilizer which differs from example 1 only in that polypyrrole, which does not include porous biochar in the preparation of the composite adsorbent, is compounded, and does not include step S3.
Comparative example 2
This comparative example provides a soil restoration compound fertilizer which differs from example 1 only in that the composite adsorbent preparation does not include phosphorylation modification of humic acid, and does not include step S5.
Experimental example
Test soil: collecting agricultural land surface soil (20-40 cm) free of heavy metal pollution in the glauber city, naturally air-drying for several days, removing impurities, grinding, sieving with a 60-mesh sieve, fully mixing the soil with CuCl 2 solution, cdCl 2 solution, K 2Cr2O7 solution and Pb (NO 3)2 solution) to obtain composite polluted soil, placing in a fume hood, and aging for 30d to obtain weathered soil;
Experimental group flowerpot: adding the soil restoration medicinal fertilizer prepared in the examples 1-3 and the comparative examples 1 and 2 according to the ratio of 0.2g/kg into weathered soil, uniformly mixing, taking 800g of polluted soil sample, and filling into a flowerpot;
flower pot of control group: taking 800g of weathered soil and putting the weathered soil into a flowerpot;
The germination accelerating treatment is carried out on the water spinach seeds, the water spinach seeds are respectively transplanted into flowerpots of an experiment group and a control group after seedling emergence, the number of plants in each pot is 5, the water spinach seed is planted in a greenhouse, the maximum water holding capacity is maintained to be 60% every day, and soil sampling can be carried out on days 1, 7, 21 and 42 in the crop growth process;
1. determination of heavy metal content in soil
Weighing 0.1g of air-dried soil sample, respectively adding 6mL of concentrated HNO 3, 2mL of concentrated HCl and 2mL of HF, digesting for 30min, placing in a microwave digestion instrument, setting the temperature at 150 ℃, keeping for 40min, taking out, sequentially carrying out operations such as acid removal, constant volume and dilution, and the like, finally measuring the content of each element by adopting AAS, and obtaining the concentration of Pb, cd, cu and Cr in the soil sample through a standard curve; the water content in the experimental soil is measured by referring to soil agrochemistry analysis (Bao Shidan 2000), and the measuring method is as follows: the pH of soil is measured by a pH meter by adopting the soil-water ratio of 1:2.5 (w/v);
analysis of results
Table 1 shows the total Pb, cd, cu and Cr contents in the soil sample, as shown in the table, the total Pb and Cr contents in the experimental soil reached 918.2mg/kg and 230.5mg/kg, respectively, and the total Cu and Cd contents were 221.3mg/kg and 4.59mg/kg, respectively; the pH of the contaminated soil was measured to be 7.1 using a pH meter.
TABLE 1 heavy metal content of contaminated soil
| Element(s) | Pb（mg/kg） | Cd（mg/kg） | Cu（mg/kg） | Cr（mg/kg） |
| Content of | 918.2 | 4.59 | 221.3 | 230.5 |
2. Determination of heavy metal content after soil remediation
(1) BCR three-step fractionation extraction: four morphological grades of heavy metals after soil remediation are determined by adopting a European Union BCR three-step grading extraction method (BCR), soil samples are collected on the 42 th day of the whole planting period for TCLP extraction, 1g of soil samples are sequentially extracted by using 0.11mol/L CH 3 COOH, 0.1mol/L hydroxylamine hydrochloride, 30% H 2O2 and 0.11mol/LNH 4 OAc, finally, the residual fraction is determined by adopting mixed acid (HNO 3、HClO4、H2O2) digestion, all solutions are pre-filtered by using a microporous filter membrane of 0.45 mu m, and the filtrate is analyzed by using an inductively coupled plasma atomic emission spectrometer (ICP-AES);
analysis of results
FIGS. 1 to 4 are diagrams showing the duty ratios of different forms of medium heavy metals Cu, cd, pb and Zn after the soil restoration medical fertilizer prepared in examples 1 to 3 and comparative examples 1 and 2 is applied; as can be seen from fig. 1 to 4, the weak acid extraction state and reducible state contents of heavy metals Cu, cd, pb and Cr in the blank group are accumulated to be more than 60%, which indicates that the experimental polluted soil has strong biotoxicity, and after the soil remediation chemical fertilizer prepared by the invention is added, the heavy metals are combined with different soil components to convert the easily soluble heavy metals into relatively stable heavy metals, and compared with the blank group, the weak acid extraction state content of Cu is reduced by about 16%, and compared with the comparative example, the weak acid extraction state content of Cu is reduced by about 10%; compared with a blank group, the weak acid extraction state content of Cd is reduced by about 12 percent, and compared with a comparative example, the weak acid extraction state content of Cd is reduced by about 10 percent; compared with the blank group, the weak acid extraction state content of Pb is reduced by about 30 percent, and compared with the comparative example, the weak acid extraction state content of Pb is reduced by about 15 percent; compared with a blank group, the weak acid extraction state content of Cr is reduced by about 45 percent, and compared with a comparative example, the weak acid extraction state content of Cr is reduced by 19 percent; from this, it can be seen that the fixing ability of Pb and Cr is the strongest in the embodiment of the present invention.
(2) Toxicity leaching extraction (TCLP) to evaluate the risk of heavy metal pollutants in the restored soil, collecting soil samples on the 1 st day, 7 th day, 21 st day and 42 th day of the whole planting period, performing TCLP extraction, weighing 1g of the soil samples, placing the soil samples into a 50ml centrifuge tube, adding 20ml of acetic acid solution with pH of 2.88, placing the centrifuge tube into a constant-temperature oscillator, sufficiently oscillating for 12 hours at the rotating speed of 60rpm, filtering the mixture by using a microporous filter membrane with the speed of 0.45 mu m, obtaining supernatant, and measuring the concentration of heavy metals in the supernatant by using an inductively coupled plasma atomic emission spectrometer (ICP-AES);
analysis of results
FIGS. 5 to 8 are graphs showing the change of the concentration of each heavy metal TCLP extracted from soil with time after application of the soil restoration medical fertilizer prepared in examples 1 to 3 and comparative examples 1 and 2 of the present invention; as can be seen from fig. 5-8, after applying the repair chemical fertilizer, the concentration of Cu, cd, pb, cr in the soil is obviously reduced, compared with the blank group, the concentration of TCLP-Cu in the embodiment of the invention is respectively reduced by about 17-20% after 42 days, and compared with the control group, the concentration of TCLP-Cu in the embodiment of the invention is respectively reduced by about 9-10% after 42 days; compared with a blank group, the TCLP-Cd concentration in the embodiment of the invention is respectively reduced by about 21-27% after 42 days, and compared with a control group, the TCLP-Cd concentration in the embodiment of the invention is respectively reduced by about 10-15% after 42 days; compared with a blank group, the TCLP-Pb concentration in the embodiment of the invention is respectively reduced by about 26-30% after 42 days, and compared with a control group, the TCLP-Pb concentration in the embodiment of the invention is respectively reduced by about 15-20% after 42 days; compared with a blank group, the TCLP-Cr concentration in the embodiment of the invention is respectively reduced by about 15-17% after 42 days, and compared with a control group, the TCLP-Cr concentration in the embodiment of the invention is respectively reduced by about 5-7% after 42 days; experiments show that the soil restoration medicine fertilizer has a stable restoration effect on Cu, cd, pb, cr.
3. The morphology and structure of the composite adsorbent prepared in example 1 of the present invention were observed by using a scanning electron microscope.
Fig. 9 is an SEM image of the composite adsorbent prepared in example 1 of the present invention.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (7)
1. A soil restoration mixed pesticide fertilizer is characterized in that: the soil remediation mixed pesticide fertilizer comprises the following components in parts by weight: 30-50 parts of a composite adsorbent, 15-20 parts of an organic fertilizer, 10-15 parts of turfy soil, 6-10 parts of urea, 15-25 parts of calcium borate, 8-12 parts of chitosan, 10-15 parts of organic acid and 1-5 parts of a water-retaining agent, wherein the composite adsorbent is polypyrrole/porous biochar composite material loaded phosphorylated humic acid;
The preparation method of the composite adsorbent specifically comprises the following steps:
S1, removing impurities from plant straws, cleaning, drying, grinding, and screening with a 60-mesh sieve to obtain plant straw powder;
S2, taking plant straw powder, soaking the plant straw powder in 20% phosphoric acid for 18-20 hours, drying the plant straw powder at 80 ℃ for 24-26 hours, putting the plant straw powder into a muffle furnace which is filled with N 2 for pyrolysis for 2-3 hours, setting the pyrolysis temperature to 500 ℃, cooling the plant straw powder, taking out a sample, washing the sample to be neutral, drying the sample at 80 ℃ for 10-12 hours, and grinding the sample to obtain activated biochar;
S3, dispersing the activated biochar prepared in the S2 in 2% glacial acetic acid solution, adding pyrrole monomer and 1mol/LFeCl 3, stirring for 3-5h, refrigerating in a refrigerator for 12-15h, regulating pH to 5.8, centrifuging at 4000r/min for 8-10min, collecting precipitate, washing, and freeze-drying to obtain polypyrrole/porous biochar composite material;
S4, adding 8mol/L nitric acid solution into humic acid, uniformly stirring, sealing and curing, washing with deionized water until the pH is 7, and naturally airing to obtain nitro humic acid;
S5, dissolving nitro humic acid in distilled water, heating to 70-75 ℃ under stirring, adding NH 4H2PO4 for reaction for 60min, cooling to room temperature, and drying at 50 ℃ for 24h to obtain modified humic acid;
s6, dissolving the modified humic acid in distilled water, adding the polypyrrole/porous biochar composite material prepared in the step S3, magnetically stirring at 180rpm for 48h, standing for 24h, washing with distilled water until the pH is 7, and freeze-drying for 24h to obtain the composite adsorbent.
2. The soil remediation mixed pesticide fertilizer of claim 1, wherein: in S1, the plant straw is one or more of rape straw, cotton straw, corn straw, bamboo straw and rice hull straw; the feed liquid ratio of the plant straw powder to the phosphoric acid is 1:10-12.
3. The soil remediation mixed pesticide fertilizer of claim 2, wherein: in S3, the feed liquid ratio of the activated biochar to the 2% glacial acetic acid solution is 1:100-150; the addition amount of the pyrrole monomer is 0.3% -0.4% of 2% glacial acetic acid solution; the molar ratio of pyrrole monomer to 1mo/LFeCl 3 is 2.5:1.
4. A soil restoration mixed fertilizer according to claim 3, which is characterized in that: in S4, the mass ratio of the humic acid to the nitric acid solution is 1:15-20.
5. The soil remediation mixed pesticide fertilizer of claim 4, wherein: in S5, the mass fraction of the nitro humic acid in distilled water is 5% -6%; the mass ratio of the nitro humic acid to the NH 4H2PO4 is 1.5-2:1.
6. The soil remediation mixed pesticide fertilizer of claim 5, wherein: in S6, the mass fraction of the modified humic acid in distilled water is 4% -5%; the mass ratio of the modified humic acid to the polypyrrole/porous biochar composite material is 1:5-6.
7. The method for preparing the soil remediation mixed pesticide fertilizer according to any one of claims 1 to 6, which is characterized in that: the method specifically comprises the following steps:
(1) Mixing the organic fertilizer, urea and calcium borate, sequentially adding turfy soil, organic acid and chitosan, and continuously stirring and mixing to obtain a first mixture;
(2) And adding the composite adsorbent and the water-retaining agent into the first mixture, and uniformly stirring to obtain the soil remediation mixed pesticide fertilizer.
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| CN108085010A (en) * | 2017-12-14 | 2018-05-29 | 青岛农业大学 | A kind of complex repairation agent and its application for heavy metal pollution of soil |
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