CN106745812B - Preparation method of strong carbon secretion type modified biochar - Google Patents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
- C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
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- 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
- C02F2101/163—Nitrates
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- 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
- C02F2101/166—Nitrites
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/16—Total nitrogen (tkN-N)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention relates to a preparation method of strong carbon secretion type modified biochar, which comprises the steps of carrying out rapid carbonization treatment on treated wetland plants at low temperature in a dry distillation mode under the protection of inert gas to obtain biochar; and mixing the biochar with 0.5-3 mol/L ferrous chloride solution, standing to load ferrous, washing, and performing anaerobic drying to obtain the strong carbon secretion type modified biochar. The preparation method provided by the invention is based on the aspect of plant resource utilization, the raw materials are sufficient and rich in types, and the wetland plants have inherent advantages compared with other biomass raw materials due to the porous characteristic. The low-temperature dry distillation preparation method is adopted, the dry distillation temperature is low, the carbonization time is short, the temperature rise is fast, and the dissolution capacity of the organic carbon is greatly higher than that of the biochar prepared at the current high temperature (>400 ℃). The method has unexpected effect on strengthening the denitrification of the artificial wetland.
Description
Technical Field
The invention relates to a preparation method of biochar, in particular to a preparation method of strong carbon-secreting type ferrous-iron-loaded modified wetland plant biochar, belonging to the technical field of environmental engineering sewage treatment
Background
As a unique composite ecological sewage treatment technology consisting of plants, matrixes, microorganisms and the like, the artificial wetland has outstanding application advantages in the standard-reaching tail water deep treatment of sewage treatment plants in developing regions, and gradually becomes one of the new methods commonly used for deep purification of sewage. However, because the carbon-nitrogen ratio in the tail water reaching the standard is low and the nitrate nitrogen content is high, the denitrification effect of the artificial wetland is often inhibited. In addition, the biomass area of wetland plants generated in China every year reaches more than five million hectares, part of the wetland plants are ingested by wetland animals and enter a biological chain, most plants wither and die directly, if a large number of wetland plants cannot be removed in time, the plants are decomposed after being corrupted and released into a wetland water body again, and the quality of the atmospheric environment is influenced by adopting an incineration method in some places. The lack of high value resource technology results in huge resource waste and potential secondary pollution risk.
The research on directly burying wetland plants into the wetland to provide a carbon source has been carried out, but the plant rotting time is difficult to control, the wetland blockage is easy to occur, the effluent chromaticity is increased, and the like. With the increasing tightening of the discharge standard of total nitrogen in sewage, how to utilize artificial wetland plant resources is an urgent need for maintaining the development of wetland ecosystem.
Biochar (Biochar) is a lamellar porous environment functional material which is generated by carbonizing biomass in a low-oxygen environment and has extremely rich carbon content and is closely stacked. In recent years, biochar is used as greenhouse gas N2The method has great application potential in aspects of O emission reduction, soil improvement and restoration, pollutant adsorption and the like, and is widely concerned. The biochar is simple and convenient to prepare, does not need to be activated, and has the cost of about 1/6 of the activated carbon. The introduction of the biochar in the artificial wetland system can provide a potential solution for realizing the resource utilization of plants and the improvement of the wetland effect at the same time.
Chinese patent document CN 104761057a discloses a biochar modular composite vertical flow constructed wetland system, which adds biochar into the concept of vertical flow constructed wetland, most biochar currently used is prepared at high temperature, most organic matters are gasified, the capability of providing carbon source is very limited, after being used for a period of time, the processing capability is reduced, therefore, a novel high carbon secretion type wetland matrix is developed, the wetland plant resource efficient utilization is realized while the wetland denitrification effect is promoted, and the system has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of strong carbon secretion type modified biochar.
The invention is realized by the following technical scheme:
a preparation method of strong carbon secretion type modified biochar comprises the following steps:
(1) cleaning wetland plants serving as raw materials, crushing the wetland plants into blocks with the diameter of 1-3 cm, air-drying the blocks to constant weight,
(2) carrying out rapid carbonization treatment on the wetland plants treated in the step (1) at a low temperature in a dry distillation mode under the protection of inert gas to obtain biochar; the dry distillation temperature is 250-400 ℃, the heating rate is 5-10 ℃/min, and the dry distillation time is 30-60 min;
(3) and load modification treatment: and (3) mixing the biochar prepared in the step (2) with 0.5-3 mol/L ferrous chloride solution, standing for 12-16 h for carrying ferrous, washing the carried biochar with deionized water to be neutral, and drying in an anaerobic environment at 100-120 ℃ for 6-12 h to obtain the strong carbon-secreting modified biochar.
In the invention, the root or stem of the wetland plant is preferably selected as the raw material in the step (1).
Preferably, the wetland plants in the step (1) are one or more than two of wetland common plants of giant reed, brocade, salix integra and the like.
Preferably, the inert gas in step (2) is nitrogen.
Preferably, the dry distillation temperature in the step (2) is 250-300 ℃, the heating rate is 5-8 ℃/min, and the dry distillation time is 40-60 min.
Most preferably, the dry distillation temperature in the step (2) is 300 ℃, the heating rate is 5-8 ℃/min, and the dry distillation time is 60 min.
According to the invention, the concentration of the ferrous chloride solution in the step (3) is preferably 1-3 mol/L, and the most preferably, the concentration of the ferrous chloride solution is 3 mol/L.
According to the invention, the loading time of the step (3) is 12 h.
According to the invention, the anaerobic drying temperature in the step (3) is preferably 100-110 ℃, the drying time is 8-12 h, and most preferably, the anaerobic drying temperature in the step (3) is 105 ℃, and the drying time is 12 h.
The strong carbon-secreting modified biochar disclosed by the invention has an unexpected effect when used for enhancing the denitrification of the constructed wetland.
The strong carbon-secreting modified charcoal is applied to strengthening the denitrification of the constructed wetland.
The specific method for using the strong carbon-secreting modified biochar to strengthen the denitrification of the constructed wetland comprises the following steps:
the strong carbon-secreting type modified biochar and a matrix are uniformly mixed and filled into the artificial wetland bed body according to the volume ratio of 1: 20-1: 4, or are used as filler columns to be embedded into the artificial wetland bed body for enhancing the denitrification and denitrification of the wetland.
In the invention, the substrate is preferably one or a mixture of more than two of gravel, construction waste bricks or quartz sand.
The raw materials and equipment used in the invention are all the prior art.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method provided by the invention is based on the aspect of plant resource utilization, the raw materials are sufficient and rich in types, and the wetland plant has inherent advantages compared with other biomass raw materials due to the porous characteristic.
(2) The preparation method adopts a low-temperature carbonization preparation method, has low carbonization temperature, short carbonization time and quick temperature rise, and greatly reduces the preparation cost compared with other biochar preparation methods.
(3) The preparation method is prepared by dry distillation at low temperature, and the dissolution capacity of the organic carbon is greatly higher than that of the biochar prepared at high temperature (>400 ℃). FIG. 1 is an organic carbon dissolution curve of Arundo donax biochar prepared by dry distillation at different temperatures, and it can be seen from the graph that organic carbon dissolution determination of the Arundo donax biochar prepared at a low temperature of 300 ℃ is carried out by deionized water according to a ratio of 1:20, the organic carbon concentration is as high as 135mg/L (2700mg/kg) which is nearly 3 times of the effluent concentration (50mg/L) of the first-class A standard COD of a sewage treatment plant, and therefore, the organic carbon plays an important role in enhanced denitrification of wastewater with a low carbon-nitrogen ratio. As the temperature rises, the dissolution amount of organic carbon in the biochar is greatly reduced, so that the high-temperature biochar has a very limited effect on releasing a carbon source and promoting denitrification.
(4) The strong carbon-secreting modified biochar has unexpected effect on strengthening the denitrification of the constructed wetland, and when the strong carbon-secreting modified biochar is applied, Fe (II) can be used as an electron donor to transfer electrons to high-valence nitrogen (such as NO)3 -，NO2 -) Oxidized in itselfMeanwhile, high-valence nitrogen can be reduced into nitrogen, so that the chemical denitrification process is realized. Meanwhile, the microorganism can also take ferrous iron and nitrate as an electron donor and an electron acceptor respectively to oxidize the ferrous iron into ferric iron and reduce the nitrate simultaneously so as to remove NO3 -Conversion to N2. In addition, when NO is present in the reaction system3 -When the consumption is finished, the microorganisms can also utilize organic matters released by the biochar to reduce Fe (III) into Fe (II), thereby realizing the redox cycle of iron-nitrogen.
Drawings
FIG. 1 is a graph of the concentration of biochar-dissolved organic carbon at different temperatures;
FIG. 2 is a schematic structural diagram of a strong carbon-secreting modified biochar prepared in example 1 of the present invention.
FIG. 3 is a bar graph of the effect of the addition of different strong carbon-secreting modified biochar on total nitrogen removal.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
Example 1
A preparation method of strong carbon secretion type modified biochar comprises the following steps:
(1) cleaning and cutting the wet plant rhizoma arundinaceae of the wet plant into blocks with the diameter of 1-3 cm, and air-drying to constant weight;
(2) carrying out rapid carbonization treatment on the wetland plants treated in the step (1) at low temperature in a dry distillation mode under the protection of nitrogen to obtain biochar; the dry distillation temperature is 300 ℃, the heating rate is 8 ℃/min, and the dry distillation time is 60 min;
(3) and load modification treatment: mixing the biochar prepared in the step (2) with 3mol/L ferrous chloride solution, standing for 12h for carrying ferrous, washing the carried biochar with deionized water to be neutral, and drying for 12h in an anaerobic environment at 105 ℃ to obtain the strong carbon-secreting type modified biochar, as shown in figure 2.
Example 2
A preparation method of strong carbon secretion type modified biochar comprises the following steps:
(1) cleaning and cutting stems of a wetland plant salix integra into blocks with the diameter of 1-3 cm, and air-drying to constant weight;
(2) carrying out rapid carbonization treatment on the wetland plants treated in the step (1) at low temperature in a dry distillation mode under the protection of nitrogen to obtain biochar; the dry distillation temperature is 250 ℃, the heating rate is 5 ℃/min, and the dry distillation time is 40 min;
(3) and load modification treatment: and (3) mixing the biochar prepared in the step (2) with 2mol/L ferrous chloride solution, standing for 14h for carrying ferrous, washing the carried biochar with deionized water to be neutral, and drying in an anaerobic environment at 100 ℃ for 12h to obtain the strong carbon-secreting modified biochar.
Example 3
A preparation method of strong carbon secretion type modified biochar comprises the following steps:
(1) cleaning and chopping the wet plant brocade stems of the wet plants into blocks with the diameter of 1-3 cm, and air-drying the wet plant brocade stems to constant weight;
(2) carrying out rapid carbonization treatment on the wetland plants treated in the step (1) at low temperature in a dry distillation mode under the protection of nitrogen to obtain biochar; the dry distillation temperature is 320 ℃, the heating rate is 8 ℃/min, and the dry distillation time is 60 min;
(3) and load modification treatment: and (3) mixing the biochar prepared in the step (2) with 2.5mol/L ferrous chloride solution, standing for 14h for carrying ferrous, washing the carried biochar with deionized water to be neutral, and drying in an anaerobic environment at 110 ℃ for 12h to obtain the strong carbon-secreting modified biochar.
Application experiments:
the modified Arundo donax Linn biochar prepared in example 1 was subjected to artificial wetland denitrification enhanced denitrification treatment.
The specific application is as follows: the strongly carbon-secreting modified biochar is used as a filler column and vertically embedded into the wetland, and the ratio of the total volume of the biochar to the volume of the wetland is 1:3 and 1:6 respectively. The packed column is a perforated column, the aperture is 0.5-1 cm, and the aperture ratio is 40-80%. The covering area of the filler columns accounts for 1/20-2/3 of the surface area of the wetland.
The wetland main body matrix filler is one or any combination of gravel, building waste bricks and fly ash, the top of the wetland main body matrix filler is paved with 15cm of coarse sand or quartz sand, and the hygrophyte is one or more combinations of bamboo reeds, brocade and salix integra.
The specific working process of the vertical flow wetland comprises the following steps:
the continuous water inlet and water outlet mode is adopted for operation. After high nitrate nitrogen sewage uniformly enters a wetland bed body 7 through a water distribution pipeline, nitrate nitrogen in inlet water is contacted with a biochar packed column in the invention, on one hand, strong carbon-secreting biochar in the invention directly promotes denitrification of denitrifying microorganisms in the sewage by releasing an organic carbon source; on the other hand, the modified biochar in the invention transfers electrons to high-valence nitrogen (such as NO) by taking surface Fe (II) as an electron donor3 -，NO2 -) The nitrogen with high valence can be reduced into nitrogen while being oxidized, so that the chemical denitrification process is realized; meanwhile, denitrifying microorganisms respectively take ferrous iron and nitrate as electron donors and acceptors to oxidize the ferrous iron into ferric iron and reduce the nitrate simultaneously to remove NO3 -Conversion to N2. The treated water is discharged out of the wetland through a water outlet.
The high-nitrate nitrogen sewage simulation wastewater enters the vertical flow wetland through the water distribution pipeline, the total nitrogen content of inlet water is 25mg/L, the pH of inlet water is 7, the inlet water load is 10L/h, denitrification treatment is carried out at the ambient temperature of 8-10 ℃, each treatment is carried out in parallel, comparison is carried out with that without biochar, under the condition of HRT (hydraulic retention time) for 5 days, the total nitrogen removal rate can reach 88%, the total nitrogen content of outlet water is less than 8mg/L, and the influence of the addition of different strong carbon type modified biochar on the total nitrogen removal effect is shown in figure 3. As can be seen from FIG. 3, the addition amount of the strong carbon-secreting modified biochar is about 30% and the treatment effect is the strongest.
Claims (4)
1. A preparation method of strong carbon secretion type modified biochar comprises the following steps:
(1) cleaning the wetland plants by taking the roots or stems of the wetland plants as raw materials, crushing the wetland plants into blocks with the diameter of 1-3 cm, air-drying the blocks to constant weight,
(2) carrying out rapid carbonization treatment on the wetland plants treated in the step (1) at low temperature in a dry distillation mode under the protection of nitrogen to obtain biochar; the dry distillation temperature is 250-300 ℃, the heating rate is 5-8 ℃/min, and the dry distillation time is 40-60 min;
(3) and load modification treatment: and (3) mixing the biochar prepared in the step (2) with 1-3 mol/L ferrous chloride solution, standing for 12 hours to load ferrous iron, washing the loaded biochar to be neutral by using deionized water, and drying for 6-12 hours in an anaerobic environment at 100-120 ℃ to obtain the strong carbon-secreting type modified biochar.
2. The preparation method of strong carbon-secreting modified biochar according to claim 1, wherein the wetland plants in step (1) are one or a mixture of more than two of wetland common plants selected from giant reed, brocade and salix integra.
3. The preparation method of strong carbon-secreting modified biochar according to claim 1, wherein the carbonization temperature in the step (2) is 300 ℃, the heating rate is 5-8 ℃/min, and the carbonization time is 60 min.
4. The preparation method of strong carbon-secreting modified biochar according to claim 1, wherein the anaerobic drying temperature in the step (3) is 100-110 ℃, and the drying time is 8-12 hours.
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| CN107743807B (en) * | 2017-10-31 | 2020-09-29 | 青岛农业大学 | Method for preventing and controlling plant root-knot nematode and fertilizing method |
| CN108059241B (en) * | 2017-12-13 | 2019-01-18 | 中国科学院地理科学与资源研究所 | A kind of extreme dehydration area basin water irrigated farmland pollutant catabolic gene method and apparatus |
| CN107892441B (en) * | 2017-12-13 | 2018-11-23 | 中国科学院地理科学与资源研究所 | Metal mine water resource recycles middle pollutant catabolic gene device and control method |
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