CN111662728B - Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof - Google Patents
Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN111662728B CN111662728B CN202010745947.0A CN202010745947A CN111662728B CN 111662728 B CN111662728 B CN 111662728B CN 202010745947 A CN202010745947 A CN 202010745947A CN 111662728 B CN111662728 B CN 111662728B
- Authority
- CN
- China
- Prior art keywords
- biochar
- walnut
- based fertilizer
- temperature
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002689 soil Substances 0.000 title claims abstract description 60
- 235000009496 Juglans regia Nutrition 0.000 title claims abstract description 52
- 235000020234 walnut Nutrition 0.000 title claims abstract description 51
- 239000003337 fertilizer Substances 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000005067 remediation Methods 0.000 title claims description 23
- 240000007049 Juglans regia Species 0.000 title description 2
- 241000758789 Juglans Species 0.000 claims abstract description 50
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 35
- 239000003610 charcoal Substances 0.000 claims abstract description 15
- 244000005700 microbiome Species 0.000 claims abstract description 14
- 241000894006 Bacteria Species 0.000 claims abstract description 13
- 230000000813 microbial effect Effects 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000001580 bacterial effect Effects 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000002503 metabolic effect Effects 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002028 Biomass Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 241000209140 Triticum Species 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 235000021307 Triticum Nutrition 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012258 culturing Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000015099 wheat brans Nutrition 0.000 description 2
- 235000006667 Aleurites moluccana Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000191938 Micrococcus luteus Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- TVBSSDNEJWXWFP-UHFFFAOYSA-N nitric acid perchloric acid Chemical compound O[N+]([O-])=O.OCl(=O)(=O)=O TVBSSDNEJWXWFP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Abstract
The invention relates to the technical field of fertilizers, in particular to a walnut branch biochar-based fertilizer soil restoration agent, a preparation method and application thereof, wherein the preparation method of the walnut branch biochar-based fertilizer soil restoration agent comprises the following steps: firstly, carbonizing walnut branches under anaerobic condition to obtain walnut branch biochar, and then mixing the dispersed biochar with the dispersed nano Fe3O4Mixed crystallization of Fe3O4The modified charcoal of the @ charcoal, and finally, the microbial colony for treating the heavy metal pollution of the soil is attached to the modified charcoal. At the moment, biochar and Fe pass through3O4The heavy metal ions in the soil are adsorbed, and pollutants are converted and degraded through the metabolic action of microbial bacteria. Not only realizes the waste utilization of walnut branches, but also uses biochar and Fe3O4And the microorganism form a system for degrading pollutants, and the heavy metal pollution of the soil is treated through the combined action of the three.
Description
Technical Field
The invention relates to the technical field of fertilizers, in particular to a walnut branch biochar-based fertilizer soil remediation agent and a preparation method and application thereof.
Background
Soil is originally a natural accommodation place and a purification treatment place for various wastes, pollutants are accommodated by the soil, and when the pollutants accommodated in the soil exceed the self-purification capacity of the soil, the soil is harmfully affected hygienically and epidemiologically, indicating that the soil is polluted. In recent years, with the continuous acceleration of the industrialization process, the mining and smelting discharge of mineral resources, the sewage irrigation and sludge application to soil are carried out, and the random discarding of solid wastes causes the soil heavy metal pollution to rise year by year, so the soil heavy metal pollution has been widely concerned.
The biomass charcoal is a solid substance rich in carbon elements and formed by high-temperature pyrolysis and carbonization of biomass under the condition of limited oxygen or no oxygen, has hydrophilic groups such as hydroxyl, carboxyl, aliphatic double bonds and the like and an aromatized structure, contains a large amount of carbon and plant nutrient substances, has a rich pore structure, a large specific surface area and more oxygen-containing active groups on the surface, and is a multifunctional material. However, the biomass charcoal also has disadvantages that the biomass charcoal can only realize physical adsorption for heavy metal ions in the soil, and cannot fundamentally remove the heavy metal ions effectively, so that the effect of treating the heavy metal contaminated soil by using the biomass charcoal alone is not ideal.
The walnut is a novel industry which is vigorously developed in rural areas in recent years, the walnut trees are pruned and shaped in the annual walnut management process, the pruned walnut branch resources are rich, but most of the pruned walnut branches are burnt as firewood at present, so that the resources are wasted, the environment is polluted, and the biomass charcoal is prepared by taking the walnut branches as raw materials, so that the waste utilization of the walnut branches is realized.
The biochar-based fertilizer soil remediation agent in the prior art only mixes biochar-based fertilizer with a water-retaining agent, inorganic salt or organic nutrients, or thoroughly decomposes biochar-based fertilizer and biomass, and realizes soil remediation by adjusting the soil structure.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide a walnut branch biochar-based fertilizer soil restoration agent and a preparation method and application thereof3O4To obtain Fe3O4The modified charcoal of the @ charcoal is prepared by adhering the microbial colony for treating the heavy metal pollution of the soil to the modified charcoal, wherein the microbial colony passes through the charcoal and Fe3O4The heavy metal ions in the soil are adsorbed, and the heavy metal pollutants are converted and degraded through the metabolic action of the microbial bacteria.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a walnut branch biochar-based fertilizer soil remediation agent comprises the following steps:
(1) preparing biochar:
a. crushing the pretreated walnut branches and sieving the crushed walnut branches with a 60-100-mesh sieve to obtain pretreated biochar;
b. under the nitrogen atmosphere, the pretreated biochar is placed in a tube furnace, the temperature is raised from room temperature to 600-plus-one temperature of 700 ℃ at the heating rate of 15 ℃/min, the temperature is kept for 2-3h, the temperature is reduced to room temperature, ball milling is carried out, and the biochar is sieved by a 120-plus-one 200-mesh sieve to obtain biochar;
(2) modification of the biochar:
a. weighing nano Fe3O4Adding nano Fe3O4Adding chloroform and performing ultrasonic treatment until a transparent and clear solution A is obtained;
b. weighing the biochar prepared in the step (1), and adding the biochar into chloroform for ultrasonic treatment until a stable solution B is formed;
c. adding the solution A into the solution B, uniformly mixing, heating for crystallization, performing suction filtration, washing and drying to obtain modified biochar, wherein the modified biochar is Fe3O4@ charcoal;
(3) and (3) adhesion and solidification of microorganisms:
mixing the microbial liquid with the modified biochar prepared in the step (2), oscillating for 40-80min at the speed of 200-220r/min at the temperature of 25-30 ℃, standing for 3-6h, and then filtering and drying the modified biochar at normal temperature to obtain the microbial-attached modified biochar;
wherein the ratio of the modified biochar to the microbial liquid is 1 g: 10-40 mL.
Preferably, in the step (1), the walnut branches are pretreated by: washing walnut branches with water to remove surface dirt, air-drying, and drying at 70-100 deg.C for 8-12 h.
Preferably, the step (2) is nano Fe3O4The mass ratio of the biological carbon to the biological carbon is 1: 5-10.
Preferably, the crystallization temperature in the step (2) is 95-120 ℃, and the crystallization time is 4-6 h.
Preferably, in the step (3), after standing for 3-6h, the mixture is continuously shaken for 60-120min, and then is filtered and dried at normal temperature after standing for 5-8 h.
Preferably, the microbial liquid in the step (3) is a mixed bacterial liquid, and the concentration of each bacterium is 1010-1014CFU/mL。
The invention also provides the walnut branch biochar-based fertilizer soil restoration agent prepared by the preparation method of the walnut branch biochar-based fertilizer soil restoration agent.
The invention also protects the application of the walnut branch biochar-based fertilizer soil restoration agent prepared by the preparation method of the walnut branch biochar-based fertilizer soil restoration agent in soil heavy metal pollution treatment.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, walnut branches are carbonized firstly, so that the walnut branch biochar which has a rich pore structure, a large specific surface area and a large number of oxygen-containing active groups on the surface is obtained, and the waste utilization of the walnut branches is realized.
2. The invention mixes and crystallizes the biochar and the ferroferric oxide to obtain Fe3O4The @ charcoal magnetic functional adsorption material physically adsorbs heavy metal ions in soil through charcoal, and Fe3O4The heavy metal ions in the soil are chemically adsorbed, and the metal ions in the soil are separated from the soil, so that the adsorption capacity is improved;
the invention obtains Fe by a crystallization method3O4@ biochar composites, Fe, in contrast to the prior art, where metal oxides were composited by impregnation3O4The combination with the biochar is firmer; because the biochar has high stability and is difficult to disappear along with the change of the surrounding environment, the Fe prepared by the invention3O4The @ charcoal can stably exist in the nature for a long time, and is used for treating soil heavy metal pollution.
3. The invention loads the microorganism on the modified biochar, so that the modified biochar provides a carrier for the microorganism to load, and simultaneously the microorganism on the modified biochar can convert and degrade heavy metal ions through the metabolism of the microorganism, so that the biochar and Fe3O4And the microorganism form a system for degrading pollutants, and the heavy metal pollution of the soil is treated through the combined action of the three.
Drawings
FIG. 1 is an XRD pattern of the modified charcoal prepared in example 2 of the present invention.
Detailed Description
The following description of the preferred embodiments and the accompanying drawings of fig. 1 are combined in detail.
The mixed bacterial liquid used in the embodiments and the related experiments of the invention is the mixed bacterial liquid of pseudoalcaligenes, micrococcus luteus and escherichia coli.
Example 1
A preparation method of a walnut branch biochar-based fertilizer soil remediation agent comprises the following steps:
(1) preparing biochar:
a. washing walnut branches with water to remove surface dirt, then air-drying, then drying at 70 ℃ for 12h, and then sieving with a 60-mesh sieve to obtain pretreated biochar;
b. under the nitrogen atmosphere, raising the temperature of the pretreated biochar from room temperature to 600 ℃ at a heating rate of 15 ℃/min in a tubular furnace, preserving the heat for 3 hours, cooling to room temperature, carrying out ball milling, and sieving with a 200-mesh sieve to obtain biochar;
(2) modification of the biochar:
a. weighing nano Fe3O4Adding nano Fe3O4Adding chloroform and performing ultrasonic treatment until a transparent and clear solution A is obtained;
b. weighing the biochar prepared in the step (1), and adding the biochar into chloroform for ultrasonic treatment until a stable solution B is formed;
c. adding the solution A into the solution B, uniformly mixing, heating and crystallizing at 95 ℃ for 6 hours, and performing suction filtration, washing and drying to obtain modified biochar, wherein the modified biochar is Fe3O4@ charcoal;
nano Fe3O4The mass ratio of the biological carbon to the biological carbon is 1: 5;
(3) and (3) adhesion and solidification of microorganisms:
mixing the mixed bacterial liquid with the modified biochar prepared in the step (2), oscillating for 80min at the speed of 200r/min at the temperature of 25 ℃, staying for 6h, continuing oscillating for 60min, staying for 8h, filtering the modified biochar, and drying at normal temperature to obtain microorganism-attached modified biochar;
wherein the ratio of the modified biochar to the mixed bacteria liquid is 1 g: 40mL, each bacteria concentration 1010CFU/mL。
Example 2
A preparation method of a walnut branch biochar-based fertilizer soil remediation agent comprises the following steps:
(1) preparing biochar:
a. washing walnut branches with water to remove surface dirt, then air-drying, then drying at 80 ℃ for 10h, and then sieving with an 80-mesh sieve to obtain pretreated biochar;
b. under the nitrogen atmosphere, raising the temperature of the pretreated biochar from room temperature to 650 ℃ at a heating rate of 15 ℃/min in a tube furnace, preserving the heat for 2.5h, cooling to room temperature, performing ball milling, and sieving with a 160-mesh sieve to obtain biochar;
(2) modification of the biochar:
a. weighing nano Fe3O4Adding nano Fe3O4Adding chloroform and performing ultrasonic treatment until a transparent and clear solution A is obtained;
b. weighing the biochar prepared in the step (1), and adding the biochar into chloroform for ultrasonic treatment until a stable solution B is formed;
c. adding the solution A into the solution B, uniformly mixing, heating and crystallizing at 110 ℃ for 5 hours, and performing suction filtration, washing and drying to obtain modified biochar, wherein the modified biochar is Fe3O4@ charcoal;
nano Fe3O4The mass ratio of the biological carbon to the biological carbon is 1: 8;
(3) and (3) adhesion and solidification of microorganisms:
mixing the mixed bacterial liquid with the modified biochar prepared in the step (2), oscillating for 60min at the speed of 200r/min at the temperature of 30 ℃, staying for 5h, continuing oscillating for 90min, staying for 7h, filtering the modified biochar, and drying at normal temperature to obtain microorganism-attached modified biochar;
wherein the ratio of the modified biochar to the mixed bacteria liquid is 1 g: 20mL, each bacteria concentration 1013CFU/mL。
Example 3
A preparation method of a walnut branch biochar-based fertilizer soil remediation agent comprises the following steps:
(1) preparing biochar:
a. washing walnut branches with water to remove surface dirt, then air-drying, then drying for 8 hours at 100 ℃, and then sieving with a 100-mesh sieve to obtain pretreated biochar;
b. under the nitrogen atmosphere, raising the temperature of the pretreated biochar from room temperature to 700 ℃ at a heating rate of 15 ℃/min in a tube furnace, preserving the heat for 2h, cooling to room temperature, carrying out ball milling, and sieving with a 120-mesh sieve to obtain biochar;
(2) modification of the biochar:
a. weighing nano Fe3O4Adding nano Fe3O4Adding chloroform and performing ultrasonic treatment until a transparent and clear solution A is obtained;
b. weighing the biochar prepared in the step (1), and adding the biochar into chloroform for ultrasonic treatment until a stable solution B is formed;
c. adding the solution A into the solution B, uniformly mixing, heating and crystallizing at 120 ℃ for 4h, and performing suction filtration, washing and drying to obtain modified biochar, wherein the modified biochar is Fe3O4@ charcoal;
nano Fe3O4The mass ratio of the biological carbon to the biological carbon is 1: 10;
(3) and (3) adhesion and solidification of microorganisms:
mixing the mixed bacterial liquid with the modified biochar prepared in the step (2), oscillating for 40min at the speed of 220r/min at the temperature of 30 ℃, staying for 3h, continuing oscillating for 120min, staying for 5h, filtering the modified biochar, and drying at normal temperature to obtain microorganism-attached modified biochar;
wherein the ratio of the modified biochar to the mixed bacteria liquid is 1 g: 10mL, each bacteria concentration 1014CFU/mL。
Comparative example 1
A preparation method of a walnut branch biochar-based fertilizer soil remediation agent comprises the following steps:
(1) preparing biochar:
a. washing walnut branches with water to remove surface dirt, then air-drying, then drying at 80 ℃ for 10h, and then sieving with an 80-mesh sieve to obtain pretreated biochar;
b. raising the temperature of the pretreated biochar from room temperature to 650 ℃ at a heating rate of 15 ℃/min in a tube furnace under the nitrogen atmosphere, preserving the heat for 2.5h, cooling to room temperature, performing ball milling, and sieving with a 160-mesh sieve to obtain the biochar.
Comparative example 2
A preparation method of a walnut branch biochar-based fertilizer soil remediation agent comprises the following steps:
(1) preparing biochar:
a. washing walnut branches with water to remove surface dirt, then air-drying, then drying at 80 ℃ for 10h, and then sieving with an 80-mesh sieve to obtain pretreated biochar;
b. under the nitrogen atmosphere, raising the temperature of the pretreated biochar from room temperature to 650 ℃ at a heating rate of 15 ℃/min in a tube furnace, preserving the heat for 2.5h, cooling to room temperature, performing ball milling, and sieving with a 160-mesh sieve to obtain biochar;
(2) modification of the biochar:
a. weighing nano Fe3O4Adding nano Fe3O4Adding chloroform and performing ultrasonic treatment until a transparent and clear solution A is obtained;
b. weighing the biochar prepared in the step (1), and adding the biochar into chloroform for ultrasonic treatment until a stable solution B is formed;
c. adding the solution A into the solution B, uniformly mixing, heating and crystallizing at 110 ℃ for 5 hours, and performing suction filtration, washing and drying to obtain modified biochar, wherein the modified biochar is Fe3O4@ charcoal.
Comparative example 3
A preparation method of a walnut branch biochar-based fertilizer soil remediation agent comprises the following steps:
(1) preparing biochar:
a. washing walnut branches with water to remove surface dirt, then air-drying, then drying at 80 ℃ for 10h, and then sieving with an 80-mesh sieve to obtain pretreated biochar;
b. under the nitrogen atmosphere, raising the temperature of the pretreated biochar from room temperature to 650 ℃ at a heating rate of 15 ℃/min in a tube furnace, preserving the heat for 2.5h, cooling to room temperature, performing ball milling, and sieving with a 160-mesh sieve to obtain biochar;
(2) and (3) adhesion and solidification of microorganisms:
mixing the mixed bacterial liquid with the biochar prepared in the step (1), oscillating for 60min at the speed of 200r/min at the temperature of 30 ℃, staying for 5h, continuing oscillating for 90min, staying for 7h, filtering the modified biochar, and drying at normal temperature to obtain microorganism-attached biochar;
wherein the ratio of the modified biochar to the mixed bacteria liquid is 1 g: 20mL, each bacteria concentration 1013CFU/mL。
Comparative example 4
The preparation method is the same as the preparation method of the embodiment 2, except that the modified biochar prepared in the step (2) is mixed with the mixed bacterial liquid in the step (3), then the mixture is shaken for 60min at the speed of 200r/min at the temperature of 30 ℃, and the mixture is kept for 5h, and then the modified biochar is filtered and dried at normal temperature to obtain the microorganism-attached modified biochar.
The walnut branch biochar-based fertilizer soil remediation agents prepared in the embodiments 1-3 of the invention can be used for treating heavy metal pollution of soil, and the soil remediation agents of the embodiments 1-3 are researched and compared with the samples of the comparative examples 1-3, and the concrete results are as follows:
FIG. 1 is an XRD (X-ray diffraction) spectrum of modified biochar prepared in example 2 of the invention, and FIG. 1 illustrates that the modified biochar prepared in example 2 not only contains main diffraction peaks of ferroferric oxide, but also contains diffraction peaks of biochar, which indicates Fe3O4@ biochar material not only contains Fe3O4Magnetic material, and containing Fe3O4The adsorption material shows that the modified biochar prepared by crystallization reaction realizes Fe3O4And compounding with biochar.
Effective viable count:
TABLE 1 effective viable cell counts loaded by samples of examples 1-3 and comparative example 3
The effective viable count is the most important index for representing the quality of the microbial fertilizer, and as can be seen from table 1, the effective viable count book conforms to and is specified by the effective viable count in standard NY/T798-2015 composite microbial fertilizer being more than or equal to 0.2 hundred million/g, and is shown by the effective viable count in table 1: the modified biochar of example 1-example 3 is loaded with mixed strains, and the composite material prepared by example 1-example 3 has certain influence on activated carbon-loaded microorganisms due to Fe3O 4. Comparative example 4 compared to the examples, the effective viable count was slightly lower than the examples, indicating that the load prone to viable bacteria remained after several shaking mixes.
Soil heavy metal pollution treatment experiment:
the repairing effect is measured by adopting a wheat seedling experimental method, wheat seeds are disinfected by medical alcohol, washed clean by deionized water, and cultured for 24 hours under the conditions of constant temperature and constant humidity, so that the germination of the seeds is promoted; then, the germinated seeds were planted in 3 test pots and 3 control pots, respectively, containing the samples of examples 1 to 3 and the heavy metal contaminated soil, respectively, and the samples of examples 1 to 3 were applied for 15 days in the test pots after the remediation, dividing the control basin into 4, respectively containing the samples of comparative examples 1-4 and heavy metal contaminated soil, applying the samples of comparative examples 1-4 in the repaired control basin for 15 days with planting density of 50 grains/basin, culturing in an incubator with temperature of 25 deg.C, illumination of 4000lx and humidity of 70-85% RH for 12h every day, taking out wheat plants after culturing for 14d, and washing the wheat bran with deionized water, drying, digesting with nitric acid-perchlorate until the wheat bran is clear and transparent, and then determining the content of heavy metals in the wheat by using an ICP-AES method. The results are shown in table 2:
the heavy metal forward movement conversion rate (heavy metal content before repair-heavy metal content after repair)/heavy metal content before repair;
TABLE 2 concentration of heavy metal ions in the soil after 15 days of fertilization
The results show that the heavy metal migration conversion capability of example 2 is best from the comparison of the heavy metal migration conversion capabilities of examples 1 to 3 in the application, and only the description shows thatIs at Fe3O4The optimal absorption conversion capability can be achieved under the condition of reasonable proportion with the biochar, and the migration conversion capability of example 3 is better when the example 1 is compared with the example 3, which shows that the content of the biochar and the Fe content are3O4The soil remediation agent obtained by increasing the content can promote the absorption of heavy metals;
comparative example 1 is charcoal and comparative example 2 is Fe3O4@ biochar, comparative example 1, had slightly less mobility conversion than comparative example 2, indicating passage of magnetic Fe3O4The heavy metal ion adsorption can be assisted, and the results show that both can carry out soil remediation, but the absorption conversion rate is lower than that of the embodiment, which shows that the heavy metal migration conversion realized by physical adsorption is slightly poor;
comparative example 3 is that the mixed strain is directly attached to the biochar, although the effective viable count of the mixed strain is more, the adsorption capacity to heavy metal is not as strong as that of the embodiment, so the heavy metal migration conversion rate of the comparative example 3 is worse than that of the embodiment;
the result shows that the migration conversion rate of the comparative example 4 is smaller than that of the examples 1 to 3 because the effective viable count of the mixed strain attached to the biochar is less in the comparative example 4.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. A preparation method of a walnut branch biochar-based fertilizer soil remediation agent is characterized by comprising the following steps:
(1) preparing biochar:
a. crushing the pretreated walnut branches, and sieving the crushed walnut branches with a 60-100-mesh sieve to obtain pretreated biochar;
b. under the nitrogen atmosphere, the pretreated biochar is placed in a tube furnace, the temperature is raised from room temperature to 600-plus-one temperature of 700 ℃ at the heating rate of 15 ℃/min, the temperature is kept for 2-3h, the temperature is reduced to room temperature, ball milling is carried out, and the biochar is sieved by a 120-plus-one 200-mesh sieve to obtain biochar;
(2) modification of the biochar:
a. weighing nano Fe3O4Adding nano Fe3O4Adding chloroform and performing ultrasonic treatment until a transparent and clear solution A is obtained;
b. weighing the biochar prepared in the step (1), and adding the biochar into chloroform for ultrasonic treatment until a stable solution B is formed;
c. adding the solution A into the solution B, uniformly mixing, heating for crystallization, performing suction filtration, washing and drying to obtain modified biochar, wherein the modified biochar is Fe3O4@ charcoal;
wherein, the nanometer Fe3O4The mass ratio of the biological carbon to the biological carbon is 1:5-10, the crystallization temperature is 95-120 ℃, and the crystallization time is 4-6 h;
(3) and (3) adhesion and solidification of microorganisms:
mixing the microbial liquid with the modified charcoal prepared in the step (2), oscillating for 40-80min at the speed of 200-220r/min at the temperature of 25-30 ℃, standing for 3-6h, filtering, and drying at normal temperature to obtain the modified charcoal with microorganism attached;
wherein the ratio of the modified biochar to the microbial liquid is 1 g: 10-40 mL;
the microbial liquid in the step (3) is a mixed bacterial liquid, and the concentration of each bacterium is 1010-1014CFU/mL。
2. The preparation method of the walnut branch biochar-based fertilizer soil remediation agent as claimed in claim 1, wherein in the step (1), the walnut branch pretreatment method comprises the following steps: washing walnut branches with water to remove surface dirt, air-drying, and drying at 70-100 deg.C for 8-12 h.
3. The method for preparing the biochar-based fertilizer soil restoration agent for walnut branches as claimed in claim 1, wherein in the step (3), the solution is kept stand for 3-6h, then is shaken for 60-120min, then is kept stand for 5-8h, and then is filtered and dried at normal temperature.
4. The walnut branch biochar-based fertilizer soil remediation agent prepared by the preparation method of the walnut branch biochar-based fertilizer soil remediation agent according to claim 1.
5. The application of the walnut branch biochar-based fertilizer soil remediation agent prepared by the preparation method of the walnut branch biochar-based fertilizer soil remediation agent according to claim 4 in soil heavy metal pollution treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010745947.0A CN111662728B (en) | 2020-07-29 | 2020-07-29 | Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010745947.0A CN111662728B (en) | 2020-07-29 | 2020-07-29 | Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111662728A CN111662728A (en) | 2020-09-15 |
| CN111662728B true CN111662728B (en) | 2021-12-21 |
Family
ID=72392909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010745947.0A Active CN111662728B (en) | 2020-07-29 | 2020-07-29 | Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111662728B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753608A (en) * | 2016-05-17 | 2016-07-13 | 北京化工大学 | Preparation method and application of novel iron-based biochar |
| KR20180028195A (en) * | 2016-09-08 | 2018-03-16 | 한국과학기술연구원 | Magnetic biochar impregnated magnetite and apparatus for fabricating the same |
| CN107824612A (en) * | 2017-11-04 | 2018-03-23 | 江西夏氏春秋环境股份有限公司 | A kind of Fe3O4The preparation method of base charcoal soil passivator |
| CN109622581A (en) * | 2018-12-28 | 2019-04-16 | 江西夏氏春秋环境股份有限公司 | A method of Heavy Metals in Soil Contaminated is removed using magnetic modification biological charcoal |
| CN110157452A (en) * | 2019-06-24 | 2019-08-23 | 贵州荣源环保科技有限公司 | A kind of heavy metal pollution of soil renovation agent |
| CN110305674A (en) * | 2019-07-10 | 2019-10-08 | 青岛农业大学 | A kind of modification biological charcoal, soil-repairing agent and its preparation method and application |
| CN110404539A (en) * | 2019-07-15 | 2019-11-05 | 上海应用技术大学 | A kind of oxidation restorative procedure of iron-based biological Pd/carbon catalyst and contaminated soil |
| CN110653246A (en) * | 2019-09-21 | 2020-01-07 | 郑州大学 | Method for removing composite pollution of heavy metal Cd and polycyclic aromatic hydrocarbon in soil |
| CN110776360A (en) * | 2019-10-30 | 2020-02-11 | 徐州得铸生物科技有限公司 | Preparation method of paddy field heavy metal soil remediation material based on biochar blended fertilizer |
| CN110899317A (en) * | 2019-12-25 | 2020-03-24 | 中国电建集团中南勘测设计研究院有限公司 | Cadmium-polluted farmland soil remediation method based on magnetic biochar |
| CN110964530A (en) * | 2018-09-29 | 2020-04-07 | 天津大学 | Soil extractant, preparation method thereof and application of soil extractant in treatment of cadmium-polluted soil |
| CN110976505A (en) * | 2019-12-17 | 2020-04-10 | 浙江省农业科学院 | Method and device for rapidly electrically repairing heavy metal contaminated soil by using magnetic biochar |
| CN111088246A (en) * | 2019-12-30 | 2020-05-01 | 东华大学 | Biochar immobilized naphthalene degrading microbial inoculum and preparation method and application thereof |
| CN111085540A (en) * | 2019-12-19 | 2020-05-01 | 浙江碧岩环保科技有限公司 | Novel material capable of separating soil pollutants and preparation process thereof |
| CN111410237A (en) * | 2020-05-09 | 2020-07-14 | 中南林业科技大学 | Resource utilization method for waste polluted biomass |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107512977B (en) * | 2017-09-07 | 2020-12-11 | 河海大学 | Preparation method and application of EM nano biochar-based soil conditioner |
| CN109622595A (en) * | 2018-12-10 | 2019-04-16 | 佛山科学技术学院 | A kind of method that charcoal repairs heavy metals in farmland pollution |
| CN109499539A (en) * | 2018-12-28 | 2019-03-22 | 天津大学 | A kind of charcoal magnetic composite and its preparation method and application |
-
2020
- 2020-07-29 CN CN202010745947.0A patent/CN111662728B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753608A (en) * | 2016-05-17 | 2016-07-13 | 北京化工大学 | Preparation method and application of novel iron-based biochar |
| KR20180028195A (en) * | 2016-09-08 | 2018-03-16 | 한국과학기술연구원 | Magnetic biochar impregnated magnetite and apparatus for fabricating the same |
| CN107824612A (en) * | 2017-11-04 | 2018-03-23 | 江西夏氏春秋环境股份有限公司 | A kind of Fe3O4The preparation method of base charcoal soil passivator |
| CN110964530A (en) * | 2018-09-29 | 2020-04-07 | 天津大学 | Soil extractant, preparation method thereof and application of soil extractant in treatment of cadmium-polluted soil |
| CN109622581A (en) * | 2018-12-28 | 2019-04-16 | 江西夏氏春秋环境股份有限公司 | A method of Heavy Metals in Soil Contaminated is removed using magnetic modification biological charcoal |
| CN110157452A (en) * | 2019-06-24 | 2019-08-23 | 贵州荣源环保科技有限公司 | A kind of heavy metal pollution of soil renovation agent |
| CN110305674A (en) * | 2019-07-10 | 2019-10-08 | 青岛农业大学 | A kind of modification biological charcoal, soil-repairing agent and its preparation method and application |
| CN110404539A (en) * | 2019-07-15 | 2019-11-05 | 上海应用技术大学 | A kind of oxidation restorative procedure of iron-based biological Pd/carbon catalyst and contaminated soil |
| CN110653246A (en) * | 2019-09-21 | 2020-01-07 | 郑州大学 | Method for removing composite pollution of heavy metal Cd and polycyclic aromatic hydrocarbon in soil |
| CN110776360A (en) * | 2019-10-30 | 2020-02-11 | 徐州得铸生物科技有限公司 | Preparation method of paddy field heavy metal soil remediation material based on biochar blended fertilizer |
| CN110976505A (en) * | 2019-12-17 | 2020-04-10 | 浙江省农业科学院 | Method and device for rapidly electrically repairing heavy metal contaminated soil by using magnetic biochar |
| CN111085540A (en) * | 2019-12-19 | 2020-05-01 | 浙江碧岩环保科技有限公司 | Novel material capable of separating soil pollutants and preparation process thereof |
| CN110899317A (en) * | 2019-12-25 | 2020-03-24 | 中国电建集团中南勘测设计研究院有限公司 | Cadmium-polluted farmland soil remediation method based on magnetic biochar |
| CN111088246A (en) * | 2019-12-30 | 2020-05-01 | 东华大学 | Biochar immobilized naphthalene degrading microbial inoculum and preparation method and application thereof |
| CN111410237A (en) * | 2020-05-09 | 2020-07-14 | 中南林业科技大学 | Resource utilization method for waste polluted biomass |
Non-Patent Citations (1)
| Title |
|---|
| Fe3O4/BC复合材料的制备及其吸附除磷性能;胡小莲等;《环境科学研究》;20180131(第1期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111662728A (en) | 2020-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | The effects of biochar addition on soil physicochemical properties: A review | |
| CN103752604B (en) | A kind of method of charcoal and Fe3+ reduction microbial inoculum renovation of heavy metal polluted soil with combined | |
| CN102276237B (en) | Attapulgite-based carbon composite ceramic particles and preparation method and use thereof | |
| CN109468307A (en) | Immobilization microorganism particles and preparation method thereof and the method that black and odorous water is efficiently administered with immobilization microorganism particles | |
| CN109536173B (en) | Composite material for simultaneously repairing heavy metal and glyphosate and preparation method thereof | |
| CN107512977B (en) | Preparation method and application of EM nano biochar-based soil conditioner | |
| CN105598158B (en) | A kind of phosphorus base biological carbon materials and its preparation and application | |
| CN110684539A (en) | Conditioner for heavy metal contaminated soil and preparation method thereof | |
| CN110523774B (en) | Method for removing lead pollution in phosphorite waste land by utilizing indigenous microorganism-plant combination | |
| CN105582890B (en) | A kind of preparation method and applications of composite Nano biomass carbon material | |
| CN106006978B (en) | The substrate improved materials and preparation method and restorative procedure of a kind of high organic bed mud shallow lake | |
| CN109821889B (en) | Soil diversified remediation method using composite material nano-microspheres | |
| CN109092873B (en) | Method for repairing arsenic-polluted soil by using plant-microorganism combination | |
| CN105689374B (en) | A kind of application of phosphorus base biological carbon materials in lead-contaminated soil improvement | |
| WO2018201733A1 (en) | Micro-ecological floating bed for aquaculture water purification and using method thereof | |
| CN103773752A (en) | Immobilized method and application of petroleum degrading bacteria | |
| CN110624948A (en) | Method for restoring cadmium-polluted soil by combining biochar and plants | |
| CN105733588B (en) | A kind of iron-based biological carbon materials and its preparation and application | |
| CN108905965A (en) | The method that sludge bioleaching-pyrolysis Combined Treatment prepares heavy metal absorbent | |
| CN108328737A (en) | A kind of Tiny ecosystem matrix, preparation method and its application based on artificial wet land reinforced processing breeding wastewater | |
| CN110922010A (en) | Benthic microorganism ecological restoration agent for black and odorous water body sediment and preparation method thereof | |
| CN111662728B (en) | Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof | |
| CN109499531B (en) | Adsorption material for domestic sewage treatment, preparation method and application thereof | |
| CN109797120B (en) | Preparation method and application of microecological preparation for removing nitrate in soil | |
| CN105176965A (en) | Preparation method for bactericide and granulous compound soil conditioner prepared from bactericide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240117 Address after: 230000 floor 1, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee after: Dragon totem Technology (Hefei) Co.,Ltd. Address before: 712100 No.24, Weihui Road, Yangling Demonstration Zone, Xianyang City, Shaanxi Province Patentee before: YANGLING VOCATIONAL & TECHNICAL College |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240410 Address after: Room 1326, Apartment Hotel, Building S2, Vanke Golden Dream Community, No. 198 Dongchi Road, Lugu Street, High tech Development Zone, Changsha City, Hunan Province, 410000 Patentee after: Hunan Yihefei Biotechnology Co.,Ltd. Country or region after: China Address before: 230000 floor 1, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee before: Dragon totem Technology (Hefei) Co.,Ltd. Country or region before: China |