CN115569644A - Biochar mixed desorption and harmless treatment method and system - Google Patents
Biochar mixed desorption and harmless treatment method and system Download PDFInfo
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- CN115569644A CN115569644A CN202211103392.5A CN202211103392A CN115569644A CN 115569644 A CN115569644 A CN 115569644A CN 202211103392 A CN202211103392 A CN 202211103392A CN 115569644 A CN115569644 A CN 115569644A
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- 238000003795 desorption Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 27
- 239000011574 phosphorus Substances 0.000 claims abstract description 27
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000012271 agricultural production Methods 0.000 claims abstract description 10
- 238000009360 aquaculture Methods 0.000 claims abstract description 8
- 244000144974 aquaculture Species 0.000 claims abstract description 8
- 150000002829 nitrogen Chemical class 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 239000004576 sand Substances 0.000 claims description 39
- 240000008042 Zea mays Species 0.000 claims description 27
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 27
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 27
- 235000005822 corn Nutrition 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 239000010902 straw Substances 0.000 claims description 18
- 238000005192 partition Methods 0.000 claims description 17
- 239000007921 spray Substances 0.000 claims description 16
- 239000004575 stone Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000005276 aerator Methods 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 3
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical class [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 241000195493 Cryptophyta Species 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 239000010907 stover Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000011084 recovery Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a method and a system for biochar mixed desorption and harmless treatment, wherein the method comprises the following steps: (1) Adding a desorbent into the biochar to be treated until the biochar to be treated is immersed by the desorbent; (2) Aerating for 1-3h, and then stopping aerating; (3) Enabling the desorbed desorbent to sequentially flow through the gravel layer, the gravel layer and the filter membrane layer and then flow out of the water outlet pipe; (4) Returning the desorbent flowing out from the step (3) to the step (1) for desorption again, and repeating the steps in this way, and desorbing for 4-6 times; (5) And (5) collecting the biochar treated in the step (4), drying the biochar for recycling, and using the desorbed desorbent for aquaculture or agricultural production. The invention uses the desorption solvent to desorb the biochar adsorbing saturated nitrogen and phosphorus, the desorption solution can be used for aquaculture industry and agricultural production, and the biochar can be repeatedly used.
Description
Technical Field
The invention relates to the field of materials, in particular to a method and a system for biochar mixed desorption and harmless treatment.
Background
Biochar is a stable, carbon-rich, solid product formed by pyrolysis of biomass under anoxic or oxygen-limited conditions. Biochar has unique characteristics such as large specific surface area, pH buffering capacity and ion exchange capacity, and is considered to be a cost-effective, environmentally friendly and highly efficient multifunctional adsorbent. Effective and environmentally friendly removal or recovery of nitrogen and phosphorus from water bodies is a significant challenge to prevent eutrophication and water quality degradation. In particular, phosphorus is an essential element of organisms, but its source is limited, scarce and has no alternatives, which may lead to depletion of readily exploitable phosphorus reserves in the near future. Therefore, phosphorus recovery will become increasingly important to support agricultural production and reduce environmental pollution pressures. Thus, the utilization of biochar to recover nitrogen and phosphorus in non-point source pollution is a considerable method for agricultural production and environmental protection.
At present, regarding the subsequent utilization of nutrients such as nitrogen and phosphorus absorbed by the biochar, the biochar with saturated absorption is usually used for improving soil, but the biochar desorption process is strongly influenced by the type of the biochar, the pH value of the environment and the type of the desorption solution, and is difficult to directly apply on an agricultural scale. And researches show that the biochar subjected to multiple adsorption-desorption cycles still has the capacity of adsorbing pollutants and can be used for multiple times. In addition, due to the complicated high-temperature preparation process, some toxic and harmful substances, such as trace metals, polycyclic Aromatic Hydrocarbons (PAHs), volatile Organic Compounds (VOCs), and small-molecule aromatic compounds substituted with hydroxyl and carboxyl groups, may remain on the biochar. Therefore, how to recycle nitrogen and phosphorus from wastewater by biochar for multiple times and realize harmless desorption is necessary.
Disclosure of Invention
The invention provides a method for biochar mixed desorption and harmless treatment thereof, and provides a system for biochar mixed desorption and harmless treatment thereof; the first object of the present invention is achieved by comprising the steps of:
(1) Adding a desorbent into the biochar to be treated until the biochar to be treated is immersed by the desorbent;
(2) Aerating for 1-3h, and then stopping aerating;
(3) Enabling the desorbed desorbent to sequentially flow through the gravel layer, the gravel layer and the filter membrane layer and then flow out of the water outlet pipe;
(4) Returning the desorbent flowing out from the step (3) to the step (1) for desorption again, and repeating the steps in this way, and desorbing for 4-6 times;
(5) And (4) collecting the biochar treated in the step (4), drying at 105 ℃ and then recycling, wherein the desorbed desorbent can be used for aquaculture or agricultural production.
Further, the biochar to be treated is biochar for adsorbing saturated nitrogen and phosphorus in nitrogen and phosphorus wastewater.
Further, the biochar is corn straw biochar, and the preparation method of the corn straw biochar comprises the following steps:
(1) Cutting corn stalk into blocks, drying, crushing, sieving with 100 mesh sieve, adding into MgCl solution containing 0.5mol/L 2 Soaking the solution in an ethylene centrifuge tube with a plug, wherein the solid-to-liquid ratio is 3:1, placing the solution in a constant temperature oscillator at 25 ℃, and oscillating at a set vibration speed of 180 r/min;
(2) And after soaking for 24 hours, taking out and filtering, drying for 24 hours in a drying oven at 105 ℃, and fully drying to obtain the corn straw biochar.
Further, the desorbent is 0.1mol/L NaOH and 0.1mol/L KCl.
Further, when the biochar to be treated adsorbs saturated ammonia nitrogen, 0.1mol/L KCl is adopted as a desorbent; and when the biochar to be treated adsorbs saturated phosphorus or adsorbs saturated nitrogen and phosphorus, 0.1mol/L NaOH is adopted as a desorbent.
The second purpose of the invention is realized in such a way that the biochar mixed desorption and harmless treatment system comprises a circular cylinder, a water inlet pipe 1, a desorbent layer 3, a biochar layer 4, a gravel layer 5, a gravel layer 6, a filter membrane layer 7, an aerator 8, a water outlet pipe 9, an air inlet pipe 10 and a partition plate 11, wherein the water inlet pipe 1 is installed at the top end of the circular cylinder, the water outlet pipe 9 is arranged at the bottom end of the circular cylinder, the desorbent layer 3, the biochar layer 4, the gravel layer 5, the gravel layer 6, the filter membrane layer 7 and the aerator 8 are sequentially arranged in the middle of the circular cylinder, the circular spray head 2 is arranged on the water inlet pipe 1, the air inlet pipe 10 is arranged in the desorbent layer 3, and the partition plate 11 is arranged between the biochar layer 4 and the gravel layer 5.
Further, the height of the desorbent layer 3 is 0.3m, the height of the biochar layer 4 is 0.8m, the height of the gravel layer 5 is 0.3m, and the height of the gravel layer 6 is 0.3m.
Furthermore, the particle size range of the broken stone in the broken stone layer 5 is 2-5mm.
Furthermore, the gravel layer 6 can be divided into a coarse sand layer, a medium sand layer and a fine sand layer from top to bottom, the heights of the coarse sand layer, the medium sand layer and the fine sand layer are respectively 0.15m, 0.1m and 0.05m, and the particle sizes of the coarse sand layer, the medium sand layer and the fine sand layer are respectively 0.5-2mm, 0.25-2mm and 0.05-0.25mm.
Furthermore, the filter membrane is made of polytetrafluoroethylene, and the aperture is 0.45 mu m.
Further, the circular nozzle 2 is an atomizing nozzle.
Further, a partition plate 11 made of stainless steel and having a thickness of 0.02m is arranged between the charcoal layer 4 and the crushed stone layer 5.
Further, the water outlet pipe 9 is provided with a drain valve 12.
The beneficial effects of the invention are:
1. the invention utilizes the biochar to effectively recover nitrogen and phosphorus in the wastewater.
2. According to the invention, according to the desorption mechanism of the biochar on nitrogen and phosphorus, by optimizing the preparation condition of the biochar and selecting the desorption solution and the environmental pH, nitrogen and phosphorus in the wastewater can be efficiently recovered, meanwhile, the leaching of toxic substances in the biochar is reduced, and the desorption solution can be used for activities such as agricultural production, aquaculture and the like.
3. The biochar still has adsorption capacity after multiple adsorption-desorption cycles and can be used for multiple times.
Drawings
FIG. 1 is a schematic diagram of the structure of the apparatus of the present invention;
in the figure, 1-a water inlet pipe, 2-a circular nozzle, 3-a desorbent layer, 4-a biochar layer, 5-a gravel layer, 6-a gravel layer, 7-a filter membrane layer, 8-an aerator, 9-a water outlet pipe, 10-an air inlet pipe, 11-a partition plate and 12-a water discharge valve.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
As shown in fig. 1, the biochar adsorbing saturated nitrogen and phosphorus is placed in a circular column, a water inlet pipe 1 is arranged above the column, the water inlet pipe 1 is connected with a circular spray head 2, a desorbent is led into the column from the circular spray head 2, the desorption time is 2 hours, the column is divided into a desorbent layer 3, a biochar layer 4, a gravel layer 5, a gravel layer 6 and a filter membrane layer 7 from top to bottom, a water outlet pipe 9 is arranged at the bottom of the filter membrane layer 7, and the desorbed solution is led out. The desorbent is 0.1mol/L of LNaOH or 0.1mol/L of KCl.
The biochar layer 4 is composed of corn straw biochar, and the preparation method is as follows:
(1) Corn stover was cut into small pieces, dried, and then pulverized to pass through a 100 mesh screen. Then adding the corn straws into a stoppered ethylene centrifuge tube containing 0.5mol/L Mg Cl2 solution for soaking, wherein the solid-to-liquid ratio is 3:1, putting the soaked corn straws into a constant temperature oscillator at 25 ℃, setting the vibration speed of 180r/min for oscillation,
(2) After soaking for 24h, taking out, filtering, drying in a drying oven at 105 ℃ for 24h, and fully drying.
(3) Placing the crucible in a muffle furnace at 500 ℃ for air burning for 2 hours, and then cooling to room temperature; taking out the crucible, weighing, then putting the corn straws which are not more than two thirds of the volume of the crucible, and recording the quality; placing the crucible in the middle of the inner cavity of the muffle furnace, introducing nitrogen (99.99%), keeping the nitrogen environment all the time, heating to 400 ℃, keeping the temperature for 4 hours, stopping heating, and weighing again after the temperature is reduced to room temperature. All biochar was stored in brown bottles and stored in a glass desiccator until use.
(4) Placing the corn stalk biochar in nitrogen and phosphorus wastewater, taking out the corn stalk biochar after adsorption saturation, drying in a drying oven at 105 ℃, taking out after 24 hours, storing in a brown bottle, and storing in a glass dryer for later use.
When the corn straw biochar is placed in nitrogen-containing wastewater, 0.1mol/L KCl is used as a desorbent; when the biochar is placed in the phosphorus-containing wastewater, 0.1mol/L NaOH is adopted as a desorbent; when the biochar is placed in nitrogen and phosphorus wastewater, 0.1mol/L NaOH is adopted as a desorbent.
The filter membrane is made of polytetrafluoroethylene, and the aperture is 0.45 mu m.
An air inlet pipe 10 is arranged below the analysis agent layer 3, and an aerator 8 is arranged on the air inlet pipe 10.
And a partition plate 11 made of stainless steel and having the thickness of 0.02m is arranged between the charcoal layer 4 and the crushed stone layer 5.
Example 1
A mixed desorption method and a harmless treatment thereof are disclosed, as shown in figure 1, comprising a water inlet pipe 1, a spray head 2, a desorbent layer 3, a biochar layer 4, a gravel layer 5, a gravel layer 6 and a filter membrane layer 7. The desorption agent is introduced from the water inlet pipe 1 and flows through the biochar layer 4, the gravel layer 5, the gravel layer 6 and the filter membrane layer 7 from top to bottom.
The biochar layer 4 is composed of corn straw biochar, and the preparation method is as follows:
(1) The crucible is placed in a muffle furnace at 500 ℃ for air burning for 2 hours and then is cooled to room temperature;
(2) Taking out the crucible, weighing, then putting the corn straws which are not more than two thirds of the volume of the crucible, and recording the quality;
(3) Placing the crucible in the middle of the inner cavity of the muffle furnace, introducing nitrogen (99.99%), keeping the nitrogen environment all the time, heating to 400 ℃, keeping the temperature for 4 hours, stopping heating, and weighing again after the temperature is reduced to room temperature. All biochar was ground using an agate mortar through a 300 mesh sieve and stored in a brown bottle;
(4) Putting the biochar into a solution with the initial ammonia nitrogen concentration of 50mg/L and the solid-to-liquid ratio of 1:5, putting the biochar into a constant-temperature shaking incubator at the temperature of 25 ℃ and the rotating speed of 160r/min, and taking out the biochar after 5 hours. And (3) measuring the nitrogen and phosphorus content of the supernatant by using a visible spectrophotometer, then placing the biochar with saturated adsorption in a 105 ℃ oven for 12 hours, drying, taking out and placing in a brown bottle for later use.
The height of the desorbent layer 3 is 0.3m, the height of the biochar layer is 0.8m, the height of the gravel layer is 0.3m, and the height of the gravel layer is 0.3m. The particle size range of the crushed stone layer 5 is 2-5mm; the gravel layer 6 can be divided into a coarse sand layer, a medium sand layer and a fine sand layer from top to bottom, the heights of the coarse sand layer, the medium sand layer and the fine sand layer are respectively 0.15m, 0.1m and 0.05m, and the particle sizes of the coarse sand layer, the medium sand layer and the fine sand layer are respectively 0.5-2mm, 0.25-2mm and 0.05-0.25mm; the material of the filter membrane is polytetrafluoroethylene, and the aperture is 0.45 mu m; the circular spray head 2 is an atomizing spray head; an air inlet pipe 10 is arranged below the desorption agent layer 3, and an aerator 8 is arranged on the air inlet pipe 10; a partition plate 11 made of stainless steel and with the thickness of 0.02m is arranged between the charcoal layer 4 and the crushed stone layer 5; the water outlet pipe 9 is provided with a drain valve 12; the desorbent was 0.1mol/L KCl.
When the device works, a desorption agent enters from the water inlet pipeline 1, is guided into the biochar layer 4 through the circular spray head 2, is provided with the partition plate 11 between the biochar layer 4 and the gravel layer 5, stops water inlet when the water level reaches the height of the desorption agent layer 3, starts aeration for 2 hours, stops aeration, extracts the partition plate, leads the desorbed water to sequentially flow through the gravel layer 5, the gravel layer 6 and the filter membrane layer 7, then flows out from the water outlet pipe 9, is guided into the water inlet pipe 1, desorbs again, and repeats the steps in the above way, after 5 times of desorption, the desorption rate of biochar to ammonia nitrogen can reach 71 percent, and the biochar is utilized in aquaculture or agricultural production to provide nutrients for algae or crops, then is collected, is dried at 105 ℃, and is stored for reuse.
Example 2
A mixed desorption method and a harmless treatment thereof are disclosed, as shown in figure 1, comprising a water inlet pipe 1, a spray head 2, a desorbent layer 3, a charcoal layer 4, a gravel layer 5, a gravel layer 6 and a filter membrane layer 7. The desorption agent is introduced from the water inlet pipe 1 and flows through the biochar layer 4, the gravel layer 5, the gravel layer 6 and the filter membrane layer 7 from top to bottom.
The biochar layer is composed of corn straw biochar, and the preparation method is as follows:
(1) Corn stover was cut into small pieces, dried, and then pulverized to pass through a 100 mesh screen. Then adding the corn straws into a stoppered ethylene centrifuge tube containing 0.5mol/L Mg Cl2 solution for soaking, wherein the solid-to-liquid ratio is 3:1, putting the soaked corn straws into a constant temperature oscillator at 25 ℃, setting the vibration speed of 180r/min for oscillation,
(2) Soaking for 24h, filtering, drying in a drying oven at 105 deg.C for 24h, and oven drying thoroughly.
(3) Placing the crucible in a muffle furnace at 500 ℃ for air burning for 2 hours, and then cooling to room temperature; taking out the crucible, weighing, then putting the corn straws which are not more than two thirds of the volume of the crucible, and recording the quality; placing the crucible in the middle of the inner cavity of the muffle furnace, introducing nitrogen (99.99%), keeping the nitrogen environment all the time, heating to 400 ℃, keeping the temperature for 4 hours, stopping heating, and weighing again after the temperature is reduced to room temperature. All biochar was stored in a brown bottle and stored in a glass desiccator until use.
(4) Putting the biochar into a solution with the initial concentration of the phosphate of 10mg/L and the solid-to-liquid ratio of 1:5, putting the biochar into a constant-temperature shaking incubator at the temperature of 25 ℃ and the rotating speed of 160r/min, and taking out the biochar after 5 hours. And (3) measuring the nitrogen and phosphorus content of the supernatant by using a visible spectrophotometer, then placing the biochar with saturated adsorption in a 105 ℃ oven for 12 hours, drying, taking out and placing in a brown bottle for later use.
The height of the desorbent layer is 0.3m, the height of the biochar layer is 0.8m, the height of the gravel layer is 0.3m, and the height of the gravel layer is 0.3m. The particle size range of the crushed stone layer is 2-5mm; the gravel layer can be divided into a coarse sand layer, a medium sand layer and a fine sand layer from top to bottom, the heights of the gravel layer are respectively 0.15m, 0.1m and 0.05m, and the particle size ranges of the gravel layer are respectively 0.5-2mm, 0.25-2mm and 0.05-0.25mm; the filter membrane is made of polytetrafluoroethylene and has a pore diameter of 0.45 mu m. The circular spray head 2 is an atomizing spray head. An air inlet pipe 10 is arranged below the analysis agent layer 3, and an aerator 8 is arranged on the air inlet pipe 10. A partition plate 11 made of stainless steel and having a thickness of 0.02m is arranged between the charcoal layer 4 and the crushed stone layer 5. The water outlet pipe 9 is provided with a drain valve 12. The desorbent was 0.1mol/L NaOH.
When the device works, a desorption agent enters from the water inlet pipeline 1, is guided into the biochar layer 4 through the circular spray head 2, is filled with the partition plate 11 between the biochar layer 4 and the gravel layer 5, stops water inlet when the water level reaches the height of the desorption agent layer 3, starts aeration for 2 hours, stops aeration, extracts the partition plate, ensures that the desorbed water sequentially flows through the gravel layer 5, the gravel layer 6 and the filter membrane layer 7, flows out from the water outlet pipe 9, is guided into the water inlet pipe 1, is desorbed again, repeats the steps in the above way, ensures that the desorption rate of biochar phosphorus can reach 75 percent after 5 times of desorption, utilizes the biochar phosphorus to provide nutrients for algae or crops in aquaculture or agricultural production, collects the biochar, dries at 105 ℃, and stores the biochar for reuse.
Example 3
A mixed desorption method and a harmless treatment thereof are disclosed, as shown in figure 1, comprising a water inlet pipe 1, a spray head 2, a desorbent layer 3, a biochar layer 4, a gravel layer 5, a gravel layer 6 and a filter membrane layer 7. The desorption agent is introduced from the water inlet pipe 1 and flows through the biochar layer 4, the gravel layer 5, the gravel layer 6 and the filter membrane layer 7 from top to bottom.
The biochar layer is composed of corn straw biochar, and the preparation method is as follows:
(1) Corn stover was cut into small pieces, dried, and then pulverized to pass through a 100 mesh screen. Then adding the corn straw to the solution containing 0.5mol/L Mg Cl 2 Soaking the solution in a centrifuge tube with a plug for ethylene with a solid-to-liquid ratio of 3:1, placing the centrifuge tube in a constant temperature oscillator at 25 ℃, oscillating at a set vibration speed of 180r/min,
(2) After soaking for 24h, taking out, filtering, drying in a drying oven at 105 ℃ for 24h, and fully drying.
(3) The crucible is placed in a muffle furnace at 500 ℃ for air burning for 2 hours and then is cooled to room temperature; taking out the crucible, weighing, then putting the corn straws which are not more than two thirds of the volume of the crucible, and recording the quality; placing the crucible in the middle of the inner cavity of the muffle furnace, introducing nitrogen (99.99%), keeping the nitrogen environment all the time, heating to 400 ℃, keeping the temperature for 4 hours, stopping heating, and weighing again after the temperature is reduced to room temperature. All biochar was stored in brown bottles and stored in a glass desiccator until use.
(4) Putting the biochar into a mixed solution with the initial concentrations of ammonia nitrogen and phosphorus phosphate of 50mg/L and 10mg/L respectively, wherein the solid-to-liquid ratio is 1:5, putting the biochar into a constant-temperature shaking incubator, wherein the temperature is 25 ℃ and the rotating speed is 160r/min, and taking out the biochar after 5 hours. And (3) measuring the nitrogen and phosphorus content of the supernatant by using a visible spectrophotometer, then placing the biochar with saturated adsorption in a 105 ℃ oven for 12 hours, drying, taking out and placing in a brown bottle for later use.
The height of the desorbent layer is 0.3m, the height of the biochar layer is 0.8m, the height of the gravel layer is 0.3m, and the height of the gravel layer is 0.3m. The particle size range of the crushed stone layer is 2-5mm; the gravel layer can be divided into a coarse sand layer, a medium sand layer and a fine sand layer from top to bottom, the heights of the coarse sand layer, the medium sand layer and the fine sand layer are respectively 0.15m, 0.1m and 0.05m, and the particle sizes of the coarse sand layer, the medium sand layer and the fine sand layer are respectively 0.5-2mm, 0.25-2mm and 0.05-0.25mm; the filter membrane is made of polytetrafluoroethylene and has a pore diameter of 0.45 mu m. The circular spray head 2 is an atomizing spray head. An air inlet pipe 10 is arranged below the analysis agent layer 3, and an aerator 8 is arranged on the air inlet pipe 10. A partition plate 11 made of stainless steel and having a thickness of 0.02m is arranged between the charcoal layer 4 and the crushed stone layer 5. The water outlet pipe 9 is provided with a drain valve 12. The desorbent was 0.1mol/L NaOH.
When the device works, a desorption agent enters from the water inlet pipeline 1, is guided into the biochar layer 4 through the circular spray head 2, is provided with the partition plate 11 between the biochar layer 4 and the gravel layer 5, stops water inlet when the water level reaches the height of the desorption agent layer 3, starts aeration for 2 hours, stops aeration, is drawn out, the desorbed water sequentially flows through the gravel layer 5, the gravel layer 6 and the filter membrane layer 7, flows out from the water outlet pipe 9, is guided into the water inlet pipe 1, is desorbed again, and repeats the steps in the above way, after 5 times of desorption, the desorption rates of the biochar to nitrogen and phosphorus respectively reach 65 percent and 71 percent, the biochar is used for providing nutrients for algae or crops in aquaculture or agricultural production, then is collected, is dried at 105 ℃, and is stored for reuse.
Claims (10)
1. A biochar mixed desorption and harmless treatment method is characterized by comprising the following steps:
(1) Adding a desorbent into the biochar to be treated until the biochar to be treated is immersed by the desorbent;
(2) Aerating for 1-3h, and then stopping aeration;
(3) Enabling the desorbed desorbent to sequentially flow through the gravel layer, the gravel layer and the filter membrane layer and then flow out of the water outlet pipe;
(4) Returning the desorbent flowing out from the step (3) to the step (1) for desorption again, and repeating the steps in this way, and desorbing for 4-6 times;
(5) And (4) collecting the biochar treated in the step (4), drying the biochar and recycling the biochar, wherein the desorbed desorbent can be used for aquaculture or agricultural production.
2. The biochar mixed desorption and harmless treatment method according to claim 1, characterized in that the biochar to be treated is biochar for adsorbing saturated nitrogen and phosphorus in nitrogen and phosphorus wastewater.
3. The biochar mixing desorption and harmless treatment method according to claim 1, characterized in that the biochar is corn stalk biochar, and the preparation method of the corn stalk biochar comprises the following steps:
(1) Cutting corn stalk into blocks, drying, crushing, sieving with 100 mesh sieve, adding into MgCl solution containing 0.5mol/L 2 Soaking the solution in an ethylene centrifuge tube with a plug, wherein the solid-to-liquid ratio is 3:1, placing the solution in a constant temperature oscillator at 25 ℃, and oscillating at a set vibration speed of 180 r/min;
(2) And after soaking for 24 hours, taking out, filtering, drying in a drying oven at 105 ℃ for 24 hours, and fully drying to obtain the corn straw biochar.
4. The biochar mixed desorption and innocent treatment method as claimed in claim 1, wherein the desorbent is 0.1mol/L NaOH or 0.1mol/L KCl.
5. The biochar mixed desorption and innocent treatment method as claimed in claim 1, characterized in that when the biochar to be treated adsorbs saturated ammonia nitrogen, 0.1mol/L KCl is adopted as a desorbent; and when the biochar to be treated adsorbs saturated phosphorus or adsorbs saturated nitrogen and phosphorus, 0.1mol/L NaOH is adopted as a desorbent.
6. The biochar hybrid desorption and harmless treatment system according to any one of claims 1 to 5, characterized by comprising a circular cylinder, a water inlet pipe (1), a desorbent layer (3), a biochar layer (4), a gravel layer (5), a gravel layer (6), a filter membrane layer (7), an aerator (8), a water outlet pipe (9), an air inlet pipe (10), a partition plate (11), the water inlet pipe (1) is installed at the top end of the circular cylinder, the water outlet pipe (9) is arranged at the bottom end of the circular cylinder, the desorbent layer (3), the biochar layer (4), the gravel layer (5), the gravel layer (6), the filter membrane layer (7) and the aerator (8) are sequentially arranged in the middle of the circular cylinder, a circular spray nozzle (2) is arranged on the water inlet pipe (1), the air inlet pipe (10) is arranged in the desorbent layer (3), and the partition plate (11) is arranged between the biochar layer (4) and the gravel layer (5).
7. The biochar hybrid desorption and harmless treatment system according to claim 6, wherein the desorbent layer (3) is 0.3m high, the biochar layer (4) is 0.8m high, the gravel layer (5) is 0.3m high, and the gravel layer (6) is 0.3m high.
8. The biochar hybrid desorption and innocent treatment system as claimed in claim 6, wherein the crushed stone in the crushed stone layer (5) has a particle size range of 2-5mm; the gravel layer (6) can be divided into a coarse sand layer, a medium sand layer and a fine sand layer from top to bottom, the heights of the coarse sand layer, the medium sand layer and the fine sand layer are respectively 0.15m, 0.1m and 0.05m, and the particle size ranges of the coarse sand layer, the medium sand layer and the fine sand layer are respectively 0.5-2mm, 0.25-2mm and 0.05-0.25mm.
9. The system for hybrid desorption and innocent treatment of biochar according to claim 6, wherein the filter membrane is made of polytetrafluoroethylene and has a pore size of 0.45 μm.
10. The biochar mixed desorption and innocent treatment system according to claim 6, wherein a partition plate (11) is arranged between the biochar layer (4) and the crushed stone layer (5), and the partition plate is made of stainless steel and is 0.02m thick.
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