CN115465851B - Synergistic application method of modified biomass carbon/humus/fertilizer conditioned red soil - Google Patents
Synergistic application method of modified biomass carbon/humus/fertilizer conditioned red soil Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 88
- 239000002689 soil Substances 0.000 title claims abstract description 71
- 239000003864 humus Substances 0.000 title claims abstract description 27
- 239000003337 fertilizer Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000001143 conditioned effect Effects 0.000 title claims description 10
- 230000002195 synergetic effect Effects 0.000 title abstract description 7
- 229920001661 Chitosan Polymers 0.000 claims abstract description 41
- 230000003750 conditioning effect Effects 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000003516 soil conditioner Substances 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 20
- 238000002791 soaking Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002309 gasification Methods 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 9
- WZLMXYBCAZZIRQ-UHFFFAOYSA-N [N].[P].[K] Chemical compound [N].[P].[K] WZLMXYBCAZZIRQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- 235000005822 corn Nutrition 0.000 claims description 6
- 210000003608 fece Anatomy 0.000 claims description 6
- 239000002921 fermentation waste Substances 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 239000002361 compost Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 5
- 239000012670 alkaline solution Substances 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000011282 treatment Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 38
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 11
- 239000011574 phosphorus Substances 0.000 abstract description 11
- 230000000087 stabilizing effect Effects 0.000 abstract description 6
- 230000001965 increasing effect Effects 0.000 abstract description 5
- 230000035558 fertility Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000002688 soil aggregate Substances 0.000 abstract description 2
- 229920000881 Modified starch Polymers 0.000 abstract 1
- 239000004368 Modified starch Substances 0.000 abstract 1
- 235000019426 modified starch Nutrition 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002686 phosphate fertilizer Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 229910021386 carbon form Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 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 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 meanwhile Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000021232 nutrient availability Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004016 soil organic matter Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000005527 soil sampling Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Soil Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Fertilizers (AREA)
Abstract
The invention belongs to the technical field of soil improvement and restoration, and relates to a synergistic application method of modified biomass carbon/humus/fertilizer conditioning red soil. After the modification, the modified starch is prepared, it has the functions of raising nitrogen content, stabilizing heavy metal, regulating soil aggregate, etc. Furthermore, the invention aims at the problems of high background value of heavy metal in red soil, imbalance of nitrogen and phosphorus elements, insufficient soil fertility and the like, and builds a synergistic application method of modified biomass carbon, humus and fertilizer based on chitosan modified biomass carbon, so as to realize the purposes of stabilizing heavy metal, adjusting nitrogen and phosphorus ratio, increasing soil fertility and improving crop yield.
Description
Technical Field
The invention relates to the technical field of soil improvement and restoration, in particular to a synergistic application method of modified biomass carbon/humus/fertilizer conditioned red soil.
Background
The provincial soil in Jiangxi, hunan, hubei and the like in China is mainly red soil, has the problems of serious acidification (pH is less than 6), high heavy metal content, low soil organic matter content (20 g/kg), serious loss of nutrient elements such as nitrogen and phosphorus and the like, and becomes one of important factors for limiting the agricultural efficient production and sustainable development in China. Therefore, the method has important practical significance for conditioning the red soil.
The addition of soil conditioners is considered to be a technical approach to effectively improving soil quality. Soil conditioners are a class of compounds that have improved physical, chemical and biological properties of the soil, and mainly include lime, mineral and industrial by-products, organic materials, and the like. Research shows that the soil conditioner has the functions of regulating the pH of soil, reducing the dosage of fertilizer, stabilizing heavy metal in soil, enhancing the biological activity of soil, improving the nutrient availability, optimizing the microbial population structure and the like. Biomass carbon is widely used for improving acid soil, saline-alkali soil, heavy metal and organic matter polluted soil due to the advantages of large specific surface area, abundant surface functional groups, wide sources, low cost and the like. The biomass carbon has obvious advantages in the aspects of nitrogen control, heavy metal stabilization and the like, but cannot rapidly improve the organic matter content of soil.
Those skilled in the art want to further improve the properties of biomass carbon and develop new soil conditioners to achieve the technical effects of improving nitrogen and phosphorus contents, stabilizing heavy metals and increasing organic content simultaneously.
Disclosure of Invention
The invention aims to provide a synergistic application method of modified biomass carbon/humus/chemical fertilizer for conditioning red soil, which can stabilize heavy metals, control nitrogen and release phosphorus, promote the fertility of the red soil and reduce the application amount of chemical fertilizer in the process of improving the red soil.
To this end, in a first aspect, the present invention provides a chitosan modified biomass carbon, and the preparation method of the chitosan modified biomass carbon includes:
s1: providing a biomass carbon source, and carrying out pyrolysis gasification under the condition of inert atmosphere or nitrogen atmosphere to prepare biomass carbon;
s2: soaking the biomass carbon with an alkali solution, and drying to obtain alkali modified biomass carbon;
s3: adding chitosan, the alkali modified biomass carbon and pentanediol into an acetic acid solution, performing a crosslinking reaction, then regulating the pH value to 9.5-10.5, standing to prepare a reactant, and washing the reactant with acetic acid and water and then drying to prepare the chitosan modified biomass carbon.
Further, in step S1, the preparation method of the biomass carbon source includes: uniformly mixing 30-45 parts of corn straw, 15-30 parts of rice husk, 20-30 parts of cow dung, 15-45 parts of fermentation waste residue and 10-15 parts of biogas residue according to parts by weight, namely a raw material of biomass carbon; and soaking the raw materials of the biomass carbon in water for 1-3 hours, and then sequentially filtering and drying to obtain the biomass carbon source.
Further, the filtration was performed using a 0.22 μm filter paper.
Further, the temperature of the drying is 55 to 65 ℃, for example 55 ℃,60 ℃, 65 ℃, etc.
In an embodiment, the biomass carbon comprises the following raw materials in parts by weight: 30 parts of corn straw, 20 parts of rice hulls, 25 parts of cow dung, 30 parts of fermentation waste residues and 15 parts of biogas residues.
Further, in the step S1, the temperature of the pyrolysis gasification is 400 to 900 ℃, for example 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, and the like; the temperature rising rate is 1-5 ℃/min, such as 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min and 5 ℃/min.
Further, in step S1, the pyrolysis and gasification time is 1 to 5 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, etc.
Further, in step S2, the alkali solution is selected from one or a combination of two of sodium hydroxide and a hydroxide solution.
Further, the concentration of the alkali solution is 0.5 to 2.5M, for example, 0.5M, 1M, 1.5M, 2M, 2.5M, etc.
Further, in step S2, the soaking process further includes the following steps: stirring.
Further, in step S2, the soaking time is 1 to 3 hours, for example, 1 hour, 2 hours, 3 hours, etc.
Further, in step S2, the temperature of the drying is 55 to 65 ℃, for example 55 ℃,60 ℃, 65 ℃ and the like.
Further, in step S3, the concentration of the acetic acid solution is 1% to 4%, for example, 1%, 2%, 3%, 4%, etc.
In the step S3, the mass ratio of the chitosan to the alkali modified biomass carbon to the pentanediol is 1-2:4-6:2-3; preferably 1:5:3.
Further, the ratio of the sum of the mass of the chitosan, the alkali modified biomass carbon and the pentanediol to the volume of the acetic acid solution is 15g/100 mL-20 g/100mL.
Further, in step S3, the time for the crosslinking is 0.5 to 1.5 hours, for example, 0.5 hours, 1 hour, 1.5 hours, etc.
Further, in step S3, the standing time is 20 to 30 hours, for example, 20 hours, 24 hours, 28 hours, 30 hours, etc.
Further, in step S3, the temperature of the drying is 75 to 85 ℃, for example, 75 ℃,80 ℃,85 ℃, etc.
The invention provides a composite soil conditioner, which comprises chitosan modified biomass carbon, humus and nitrogen-phosphorus-potassium ternary compound fertilizer.
Further, the humus is a living garbage compost product.
Further, the weight ratio of the chitosan modified biomass carbon to the humus is 1-5:5-9; preferably 3:7.
Further, the mass ratio of the sum of the chitosan modified biomass carbon and the humus to the nitrogen-phosphorus-potassium ternary compound fertilizer is 1-9:1-9; preferably 4:6.
In a third aspect of the invention there is provided a method of conditioning soil comprising applying to the soil to be conditioned a composite soil conditioner according to the second aspect of the invention.
Further, the dosage of the compound soil conditioner is 0.5 to 5.0 weight percent of the soil to be conditioned; for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 4%, etc.
Further, the application depth of the composite soil conditioner is 0-10 cm of the surface layer of the soil to be conditioned.
According to the invention, the traditional biomass carbon is modified, so that the functions of nitrogen control and heavy metal stabilization are enhanced. On the basis, the invention introduces humus and chemical fertilizer to make up for the shortage of biomass carbon in terms of organic matter regulation. Through the combined application of the three, the effects of stabilizing heavy metals, controlling nitrogen and phosphorus, improving the fertility of the red soil, reducing the application amount of chemical fertilizers and the like in the improvement process of the red soil are effectively improved, and the red soil has good market application potential.
The basic principle of the invention is as follows: the composite soil conditioner consists of three parts of modified biomass carbon, humus, nitrogen-phosphorus-potassium ternary compound fertilizer. The chitosan modified biomass carbon has rich hanging energy groups and pore canal structures on the surface, so that the chitosan modified biomass carbon has excellent adsorption complexing effect on heavy metals and nitrogen in soil, meanwhile, soil aggregate particles are improved, and the living microenvironment of microorganisms is optimized; the humus is widely distributed in soil, has a high molecular net structure, and has the effects of activating phosphate fertilizer, complexing heavy metal and improving the organic matter content of the soil; the nitrogen-phosphorus-potassium ternary compound fertilizer has the function of improving the effective nitrogen, quick-acting phosphorus and fertilizer of soil. Aiming at the red soil pollution characteristics, the modified biomass carbon, humus and chemical fertilizer are organically combined, the proportion of the modified biomass carbon, the humus and the chemical fertilizer is regulated, the application method is optimized, the application amount of the chemical fertilizer is reduced, and the repair of the heavy metal polluted red soil and the improvement of the quality of the red soil are realized.
Compared with the prior art, the technical scheme of the invention has the following steps:
(1) According to the chitosan modified biomass carbon provided by the invention, the chitosan modified biomass carbon is modified to form a rich pore structure, chitosan particles appear on the surface, the variety of surface functional groups is increased, and the stabilizing capability of the chitosan modified biomass carbon on substances such as nitrogen, heavy metals and the like is further improved. The biomass carbon and chitosan modified material used in the invention has wide sources, simple preparation method and low cost, is suitable for large-scale production, and does not cause secondary pollution to soil environment.
(2) The invention provides a composite soil conditioner, wherein three components of modified biomass carbon, humus and nitrogen-phosphorus-potassium ternary compound fertilizer are mutually matched, and the humus and the modified biomass carbon form a synergistic effect in the aspects of activating phosphate fertilizer, improving the utilization rate of phosphate fertilizer, complexing stable heavy metal, enhancing the activity of microorganisms and the like. Hydrophilic components and fulvic acid substances in humus enhance migration of heavy metals in soil, hydrophobicity and humus substances improve solidification level of the heavy metals in soil, aging and stabilization of the heavy metals are accelerated, bioavailability and mobility of the heavy metals are reduced, risks of pollution of heavy metals in soil to plants and groundwater are reduced, and grain safety is guaranteed.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. In the drawings:
FIG. 1 is a surface micro-morphology of unmodified biomass carbon;
FIG. 2 shows the microscopic morphology of the chitosan modified biomass carbon surface provided by the invention;
FIG. 3 is an infrared test result of chitosan modified biomass carbon provided by the invention;
fig. 4 shows the growth of a plant in red soil to which the composite soil conditioner provided by the present invention is applied.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Example 1
Uniformly mixing 30 parts of corn stalks, 20 parts of rice hulls, 25 parts of cow dung, 30 parts of fermentation waste residues and 15 parts of biogas residues, soaking the mixture in deionized water for 1h, filtering the mixture, and drying the mixture at 60 ℃ to obtain a biomass carbon source. And (3) placing the biomass carbon source in a nitrogen atmosphere, and carrying out pyrolysis gasification for 5 hours at 800 ℃ with a heating rate of 2 ℃/min to obtain biomass carbon.
And soaking the biomass carbon for 1h by using a 1M sodium hydroxide solution, fully stirring, and drying at 60 ℃ to obtain the sodium hydroxide modified biomass carbon.
Mixing 1g of chitosan with 50mL of acetic acid solution with mass concentration of 2%, adding 5g of sodium hydroxide modified biomass carbon, adding 3g of pentanediol, and crosslinking for 1h; and then regulating the pH value of the solution to 10 by using sodium hydroxide, standing for 24 hours, rinsing the precipitate with acetic acid and deionized water for 3 times, and drying at 80 ℃ to obtain the chitosan modified biomass carbon.
Scanning electron microscope imaging is respectively carried out on an unmodified biomass carbon source and the prepared chitosan modified biomass carbon, imaging results are respectively shown in fig. 1 and fig. 2, after modification, the chitosan modified biomass carbon forms a pore structure, chitosan particles appear on the surface, and the variety of surface functional groups is increased, so that the successful synthesis of the chitosan modified biomass carbon is illustrated.
Infrared tests are respectively carried out on the unmodified biomass carbon source and the prepared chitosan modified biomass carbon, and the test results are shown in figure 3.
Example 2
Uniformly mixing 45 parts of corn stalks, 15 parts of rice hulls, 20 parts of cow dung, 45 parts of fermentation waste residues and 12 parts of biogas residues, soaking the mixture in deionized water for 2 hours, filtering the mixture, and drying the mixture at 65 ℃ to obtain a biomass carbon source. And (3) placing the biomass carbon source in a nitrogen atmosphere, and carrying out pyrolysis gasification for 5 hours at the temperature of 500 ℃ at the heating rate of 1 ℃/min to obtain the biomass carbon.
And soaking the biomass carbon for 1h by using a 2.5M sodium hydroxide solution, fully stirring, and drying at 60 ℃ to obtain the sodium hydroxide modified biomass carbon.
Mixing 2g of chitosan with 50mL of acetic acid solution with mass concentration of 2%, adding 4g of sodium hydroxide modified biomass carbon, adding 3g of pentanediol, and crosslinking for 1h; and then regulating the pH value of the solution to 10 by using sodium hydroxide, standing for 20 hours, rinsing the precipitate with acetic acid and deionized water for 3 times, and drying at 75 ℃ to obtain the chitosan modified biomass carbon.
Example 3
Uniformly mixing 35 parts of corn stalks, 30 parts of rice hulls, 30 parts of cow dung, 15 parts of fermentation waste residues and 10 parts of biogas residues, soaking the mixture in deionized water for 3 hours, filtering the mixture, and drying the mixture at 55 ℃ to obtain a biomass carbon source. And (3) placing the biomass carbon source in a nitrogen atmosphere, and carrying out pyrolysis gasification for 1h at 900 ℃ with a heating rate of 5 ℃/min to obtain biomass carbon.
And soaking the biomass carbon for 3 hours by using a 0.5M sodium hydroxide solution, fully stirring, and drying at 60 ℃ to obtain the sodium hydroxide modified biomass carbon.
Mixing 1g of chitosan with 50mL of acetic acid solution with mass concentration of 2%, adding 6g of sodium hydroxide modified biomass carbon, adding 2g of pentanediol, and crosslinking for 1h; and then regulating the pH value of the solution to 10 by using sodium hydroxide, standing for 28h, rinsing the precipitate with acetic acid and deionized water for 3 times, and drying at 85 ℃ to obtain the chitosan modified biomass carbon.
Example 4
The chitosan modified biomass carbon prepared in the example 1 is taken, and is evenly mixed with humus (domestic garbage compost product) and nitrogen-phosphorus-potassium ternary compound fertilizer to prepare the composite soil conditioner.
Preparing a composite soil conditioner with a component ratio of a to b (c), wherein a to b is the mass ratio of chitosan modified biomass carbon to humus; (c) The mass percentage of the composite soil conditioner is the sum of the mass of chitosan modified biomass carbon and humus. a. The values of b and c are shown in tables 1 to 5.
Soil sampling was performed from Fuzhou city current pit village as red soil to be improved, and the quality detection results were as follows: 13.0g/kg of organic matters, 43.6mg/kg of Pb, 38.6mg/kg of Cr, 0.10mg/kg of Cd, 250mg/kg of N, 386mg/kg of P, 3053 mg/kg of K, 0.70mg/kg of available phosphorus, 326mg/kg of quick-acting potassium, 9.00mg/kg of alkaline hydrolysis nitrogen and pH 6.02.
And (3) adding the prepared composite soil conditioner to the surface layer of the red soil to be improved by 0-5 cm, wherein the dosage of the composite soil conditioner is 3.0wt% of the soil to be conditioned. Meanwhile, a control group 1 for soil conditioning by only humus and a control group 2 for soil conditioning by only chitosan modified biomass carbon are arranged.
After adding the soil conditioner to the red soil to be improved, soil leaching (to simulate the condition of multiple soil component loss caused by multiple rainfall in nature) and detection are carried out on the 7 th day, the 14 th day, the 21 st day and the 28 th day. Wherein, the nitrogen and Pb in the soil leaching solution measured on the 28 th day 2+ The results of the ion, available nitrogen, available phosphorus concentration and organic content measurements are shown in tables 1-5, respectively.
TABLE 1 variation of Nitrogen concentration (mg/L) in various experimental groups of leaching solutions
Control group 1:0.412mg/L; control group 2:0.109mg/L.
TABLE 2 different experimental groups drenched Pb in solution 2+ Ion concentration Change (mg/L)
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(10％) | 0.336 | 1:9(20％) | 0.312 | 1:9(30％) | 0.285 |
| 2:8(10％) | 0.009 | 2:8(20％) | 0.028 | 2:8(30％) | 0.027 |
| 3:7(10％) | 0.075 | 3:7(20％) | 0.010 | 3:7(30％) | 0.013 |
| 4:6(10％) | 0.078 | 4:6(20％) | 0.125 | 4:6(30％) | 0.090 |
| 5:5(10％) | 0.097 | 5:5(20％) | 0.029 | 5:5(30％) | 0.071 |
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(40％) | 0.248 | 1:9(50％) | 0.072 | 1:9(60％) | 0.325 |
| 2:8(40％) | 0.015 | 2:8(50％) | 0.114 | 2:8(60％) | 0.033 |
| 3:7(40％) | 0.008 | 3:7(50％) | 0.082 | 3:7(60％) | 0.014 |
| 4:6(40％) | 0.025 | 4:6(50％) | 0.044 | 4:6(60％) | 0.122 |
| 5:5(40％) | 0.140 | 5:5(50％) | 0.093 | 5:5(60％) | 0.018 |
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(70％) | 0.288 | 1:9(80％) | 0.264 | 1:9(90％) | 0.252 |
| 2:8(70％) | 0.017 | 2:8(80％) | 0.031 | 2:8(90％) | 0.028 |
| 3:7(70％) | 0.051 | 3:7(80％) | 0.055 | 3:7(90％) | 0.045 |
| 4:6(70％) | 0.039 | 4:6(80％) | 0.040 | 4:6(90％) | 0.041 |
| 5:5(70％) | 0.100 | 5:5(80％) | 0.056 | 5:5(90％) | 0.068 |
Control group 1:0.384mg/L; control group 2:0.133mg/L.
TABLE 3 effective Nitrogen concentration variation (mg/g) in soil for different experimental groups
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(10％) | 342 | 1:9(20％) | 289 | 1:9(30％) | 858 |
| 2:8(10％) | 390 | 2:8(20％) | 369 | 2:8(30％) | 652 |
| 3:7(10％) | 150 | 3:7(20％) | 172 | 3:7(30％) | 769 |
| 4:6(10％) | 127 | 4:6(20％) | 271 | 4:6(30％) | 951 |
| 5:5(10％) | 339 | 5:5(20％) | 421 | 5:5(30％) | 915 |
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(40％) | 1024 | 1:9(50％) | 699 | 1:9(60％) | 1465 |
| 2:8(40％) | 1775 | 2:8(50％) | 936 | 2:8(60％) | 547 |
| 3:7(40％) | 1608 | 3:7(50％) | 1019 | 3:7(60％) | 706 |
| 4:6(40％) | 1149 | 4:6(50％) | 799 | 4:6(60％) | 755 |
| 5:5(40％) | 1812 | 5:5(50％) | 1042 | 5:5(60％) | 816 |
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(70％) | 250 | 1:9(80％) | 846 | 1:9(90％) | 741 |
| 2:8(70％) | 213 | 2:8(80％) | 1033 | 2:8(90％) | 834 |
| 3:7(70％) | 403 | 3:7(80％) | 774 | 3:7(90％) | 1240 |
| 4:6(70％) | 348 | 4:6(80％) | 812 | 4:6(90％) | 1196 |
| 5:5(70％) | 681 | 5:5(80％) | 859 | 5:5(90％) | 1080 |
Control group 1:215mg/g; control group 2:307mg/g.
TABLE 4 variation of effective phosphorus concentration (mg/g) in soil for different experimental groups
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(10％) | 159 | 1:9(20％) | 732 | 1:9(30％) | 158 |
| 2:8(10％) | 449 | 2:8(20％) | 257 | 2:8(30％) | 123 |
| 3:7(10％) | 632 | 3:7(20％) | 186 | 3:7(30％) | 322 |
| 4:6(10％) | 489 | 4:6(20％) | 584 | 4:6(30％) | 109 |
| 5:5(10％) | 154 | 5:5(20％) | 498 | 5:5(30％) | 254 |
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(40％) | 679 | 1:9(50％) | 65 | 1:9(60％) | 73 |
| 2:8(40％) | 719 | 2:8(50％) | 152 | 2:8(60％) | 193 |
| 3:7(40％) | 1136 | 3:7(50％) | 207 | 3:7(60％) | 115 |
| 4:6(40％) | 806 | 4:6(50％) | 167 | 4:6(60％) | 164 |
| 5:5(40％) | 1346 | 5:5(50％) | 95 | 5:5(60％) | 64 |
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(70％) | 386 | 1:9(80％) | 346 | 1:9(90％) | 924 |
| 2:8(70％) | 349 | 2:8(80％) | 279 | 2:8(90％) | 835 |
| 3:7(70％) | 800 | 3:7(80％) | 192 | 3:7(90％) | 556 |
| 4:6(70％) | 940 | 4:6(80％) | 274 | 4:6(90％) | 528 |
| 5:5(70％) | 1594 | 5:5(80％) | 107 | 5:5(90％) | 876 |
Control group 1:1324mg/g; control group 2:737mg/g.
TABLE 5 variation of organic matter content (mg/g) in soil for different experimental groups
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(10％) | 19.8 | 1:9(20％) | 12.2 | 1:9(30％) | 13.0 |
| 2:8(10％) | 22.3 | 2:8(20％) | 19.0 | 2:8(30％) | 16.0 |
| 3:7(10％) | 12.1 | 3:7(20％) | 27.9 | 3:7(30％) | 20.0 |
| 4:6(10％) | 18.9 | 4:6(20％) | 15.8 | 4:6(30％) | 16.0 |
| 5:5(10％) | 25.4 | 5:5(20％) | 20.7 | 5:5(30％) | 23.0 |
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(40％) | 32.1 | 1:9(50％) | 15.3 | 1:9(60％) | 15.35 |
| 2:8(40％) | 23.6 | 2:8(50％) | 12.0 | 2:8(60％) | 21.75 |
| 3:7(40％) | 33.0 | 3:7(50％) | 20.1 | 3:7(60％) | 33.95 |
| 4:6(40％) | 17.0 | 4:6(50％) | 21.8 | 4:6(60％) | 16.35 |
| 5:5(40％) | 28.0 | 5:5(50％) | 17.9 | 5:5(60％) | 19.35 |
| Group/a b (c) | Concentration of | Group/a b (c) | Concentration of | Group/a b (c) | Concentration of |
| 1:9(70％) | 10.15 | 1:9(80％) | 12.7 | 1:9(90％) | 17.4 |
| 2:8(70％) | 21.95 | 2:8(80％) | 19.4 | 2:8(90％) | 28.6 |
| 3:7(70％) | 23.75 | 3:7(80％) | 22.6 | 3:7(90％) | 15.3 |
| 4:6(70％) | 27.15 | 4:6(80％) | 18.7 | 4:6(90％) | 17.8 |
| 5:5(70％) | 32.15 | 5:5(80％) | 19.9 | 5:5(90％) | 24.1 |
Control group 1:29.38mg/g; control group 2:16.09mg/g.
According to the results, after the composite soil conditioner provided by the invention is used for conditioning red soil, nitrogen (table 1) and Pb in the soil leaching solution 2+ The concentration of ions (table 2) was significantly reduced and the contents of available nitrogen (table 3), available phosphorus (table 4) and organic matter (table 5) in the soil were significantly increased. The excellent effect of the composite soil conditioner for conditioning the heavy metal polluted red soil is shown.
The composite soil conditioner with a ratio of a to b (c) of 3:7 (60%) is added on the surface layer of the red soil for 0-5 cm, and the plant growth vigor is observed (meanwhile, a control of the non-improved red soil is arranged), the observation result is shown in fig. 4, and according to fig. 4, the plant planted in the improved red soil has more excellent growth vigor compared with the non-improved red soil.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (19)
1. A composite soil conditioner is characterized by comprising chitosan modified biomass carbon, humus and a nitrogen-phosphorus-potassium ternary compound fertilizer; the weight ratio of the chitosan modified biomass carbon to the humus is (2:8) - (3:7); the ratio of the sum of the mass of the chitosan modified biomass carbon and the mass of the humus to the mass of the nitrogen-phosphorus-potassium ternary compound fertilizer is 4:6;
the preparation method of the chitosan modified biomass carbon comprises the following steps:
s1: providing a biomass carbon source, and carrying out pyrolysis gasification under the condition of inert atmosphere or nitrogen atmosphere to prepare biomass carbon;
s2: soaking the biomass carbon with an alkali solution, and drying to obtain alkali modified biomass carbon;
s3: adding chitosan, alkali modified biomass carbon and pentanediol into an acetic acid solution, performing a crosslinking reaction at a mass ratio of 1-2:4-6:2-3, regulating pH to 9.5-10.5, standing to prepare a reactant, and washing the reactant with acetic acid and water and drying to prepare the chitosan modified biomass carbon.
2. The composite soil conditioner of claim 1, wherein in step S1, the method for preparing the biomass carbon source comprises: uniformly mixing 30-45 parts of corn stalks, 15-30 parts of rice hulls, 20-30 parts of cow dung, 15-45 parts of fermentation waste residues and 10-15 parts of biogas residues according to parts by weight, namely a raw material for biomass carbon sources; and soaking the raw materials of the biomass carbon source in water for 1-3 hours, and then sequentially filtering and drying to obtain the biomass carbon source.
3. The composite soil conditioner of claim 2, wherein the filtration is performed using 0.22 μm filter paper.
4. The composite soil conditioner of claim 1, wherein in step S1, the temperature of pyrolysis gasification is 400-900 ℃; the temperature rising rate is 1-5 ℃/min.
5. The composite soil conditioner of claim 1, wherein in step S1, the pyrolysis gasification time is 1 to 5 hours.
6. The composite soil conditioner of claim 1, wherein in step S2, the alkaline solution is selected from one or a combination of two of sodium hydroxide and a hydroxide solution.
7. The composite soil conditioner of claim 6, wherein the concentration of the alkaline solution is 0.5-2.5M.
8. The composite soil conditioner of claim 1, wherein in step S2, the soaking process further comprises the following treatments: stirring.
9. The composite soil conditioner of claim 1, wherein in step S2, the soaking time is 1-3 hours.
10. The composite soil conditioner of claim 1, wherein in step S2, the temperature of the drying is 55-65 ℃.
11. The composite soil conditioner of claim 1, wherein in step S3, the concentration of the acetic acid solution is 1% -4%.
12. The composite soil conditioner of claim 1, wherein the ratio of the sum of the mass of chitosan, alkali modified biomass carbon and pentanediol to the volume of the acetic acid solution is 15g/100ml to 20g/100mL.
13. The composite soil conditioner of claim 1, wherein in step S3, the time of crosslinking is 0.5 to 1.5 hours.
14. The composite soil conditioner of claim 1, wherein in step S3, the time of standing is 20 to 30 hours.
15. The composite soil conditioner of claim 1, wherein in step S3, the temperature of the drying is 75-85 ℃.
16. The composite soil conditioner of claim 1, wherein the humus is a living waste compost product.
17. A method of conditioning soil comprising applying the composite soil conditioner of any one of claims 1 to 16 to the soil to be conditioned.
18. The soil conditioning method of claim 17, wherein the amount of the composite soil conditioner is 0.5 to 5.0wt% of the soil to be conditioned.
19. The soil conditioning method according to claim 17, wherein the application depth of the composite soil conditioner is 0-10 cm of the surface layer of the soil to be conditioned.
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