CN112194244B - Lanthanum-modified constructed wetland biochar substrate prepared by hydrothermal method and preparation method thereof - Google Patents
Lanthanum-modified constructed wetland biochar substrate prepared by hydrothermal method and preparation method thereof Download PDFInfo
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- CN112194244B CN112194244B CN202010856690.6A CN202010856690A CN112194244B CN 112194244 B CN112194244 B CN 112194244B CN 202010856690 A CN202010856690 A CN 202010856690A CN 112194244 B CN112194244 B CN 112194244B
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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
- C02F3/28—Anaerobic digestion processes
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
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- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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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
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Abstract
The invention provides a lanthanum-modified constructed wetland biochar substrate prepared by a hydrothermal method and a preparation method thereof, and the lanthanum-modified constructed wetland biochar substrate comprises the following steps: drying, cleaning, drying and chopping the straws of the wetland plants, putting the straws into a hydrothermal reaction kettle, and adding a mixed aqueous solution of ammonia water and lanthanum chloride; carrying out hydrothermal carbonization treatment on the hydrothermal reaction kettle in an oxygen-limited environment; and after the hydrothermal carbonization treatment reaction is finished, filtering and separating precipitates, washing the precipitates with deionized water, and drying the precipitates to constant weight to obtain the lanthanum-modified constructed wetland biochar by a hydrothermal method, wherein the lanthanum-modified constructed wetland biochar is used as a constructed wetland matrix.
Description
Technical Field
The invention belongs to the technical field of sewage treatment and waste plant recycling, and particularly relates to a lanthanum-modified constructed wetland biochar substrate prepared by a hydrothermal method and a preparation method thereof.
Background
The statements in this section merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The problem of water eutrophication is more and more common and aggravated, and the eutrophication refers to the phenomenon of water quality pollution caused by excessive content of plant nutrient substances such as nitrogen, phosphorus and the like in water bodies such as lakes, rivers, reservoirs and the like. As a limiting nutrient element of eutrophic water, removal of phosphorus has been a major problem to be studied. The eutrophication concentration of the phosphorus (more than 0.01-0.02 ppm) is far lower than the standard concentration of sewage discharge (less than 0.1mg/L), so that deep purification of the phosphorus in the sewage is very necessary.
The artificial wetland is a common advanced sewage treatment technology, and can remove phosphorus through the combined action of aquatic plants, substrates and microorganisms. Research proves that more than 70 percent of phosphorus in the artificial wetland is removed through the adsorption of the substrate. Therefore, the research and development of the high-efficiency dephosphorization wetland substrate is the key for strengthening the dephosphorization of the artificial wetland.
As a common adsorbent, the biochar has the advantages of rich surface functional groups, large specific surface area, good adsorption performance, stable property, good reproducibility and the like. The biochar is used as a wetland improvement matrix and has a good application prospect. The biochar can capture and fix nitrogen, phosphorus and other plant essential nutrients, promote plant growth, and provide sufficient attachment points and denitrification carbon sources for microorganisms. Wetland plants are good raw materials for preparing biochar, on one hand, wetland plants contain rich biomass, high-content cellulose and hemicellulose in the biomass contribute to the formation of the biochar, on the other hand, the resource utilization of waste wetland plants is still limited at present, and withered wetland plants are easy to block artificial wetlands in winter, so that the maintenance and operation of the wetlands are influenced. Therefore, the biochar is prepared by taking wetland plants as raw materials and is backfilled to the artificial wetland, so that not only can an excellent artificial wetland matrix be obtained, but also the resource utilization of the waste plants of the artificial wetland can be realized. However, functional groups on the surface of the biochar are mainly negatively charged, have poor affinity to phosphate radicals and have limited specificity adsorption capacity to phosphorus when directly used.
The inventor finds that the cheap rare earth metal lanthanum can be combined with phosphate radical through inner layer complexation, chemical precipitation, electrostatic attraction and the like to form a stable complex compound, so that the phosphate in water can be removed. Research has proved that lanthanum is loaded on the biochar, so that the high-efficiency phosphorus removal capability of the biochar can be obviously enhanced. However, the existing lanthanum loading mode is easy to have the problems of weak combination, uneven loading and the like, and the existing lanthanum loading mode has many operation steps and cannot be synthesized in one step.
Disclosure of Invention
In order to overcome the defects of the prior art, the lanthanum-modified biochar matrix prepared by a hydrothermal method and a preparation method thereof are provided, lanthanum is loaded on biochar which takes wetland plants as raw materials in the form of water and oxides by a one-step synthesis hydrothermal method, so that the constructed wetland biochar matrix capable of efficiently and exclusively adsorbing phosphorus is obtained, and the matrix can provide a slow-release carbon source for the denitrification process of microorganisms.
In order to achieve the above object, one or more embodiments of the present disclosure provide the following technical solutions:
in a first aspect, a preparation method of a lanthanum-modified constructed wetland biochar substrate by a hydrothermal method is disclosed, and comprises the following steps:
drying, cleaning, drying and chopping the straws of the wetland plants, putting the straws into a hydrothermal reaction kettle, and adding a mixed aqueous solution of ammonia water and lanthanum (lanthanum chloride heptahydrate);
carrying out hydrothermal carbonization reaction on the mixture in an oxygen-limited environment of a hydrothermal reaction kettle for a certain time at a certain temperature;
and after the hydrothermal carbonization reaction is finished, filtering and separating precipitates, washing the precipitates with deionized water, and drying the precipitates to constant weight to obtain the hydrothermal lanthanum modified biochar, namely the hydrothermal lanthanum biochar for short, which is used as a substrate of the artificial wetland.
According to a further technical scheme, the mass ratio of the wetland plant straws to the lanthanum element is 1:0.05-0.1, the mass ratio of the wetland plant straws to the ammonia water is 1:0.3-1, and the mass ratio of the wetland plant straws to pure water is 1: 10-20. The ammonia water not only adds surface nitrogen functional groups for the biochar, but also provides an alkaline environment, so that lanthanum is tightly complexed with the biochar in a hydrated oxidation state.
In the further technical scheme, the hydrothermal reaction kettle is subjected to hydrothermal carbonization treatment in an oxygen-limited environment, the reaction temperature is 200-300 ℃, and the reaction time is 10-20 hours.
In a second aspect, the lanthanum-modified constructed wetland biochar substrate prepared by the hydrothermal method is disclosed. The components of the biochar substrate comprise 20% of biochar and 80% of other conventional substrates.
In a further aspect, the conventional substrate includes, but is not limited to, one of quartz sand, zeolite, or gravel.
The above one or more technical solutions have the following beneficial effects:
according to the technical scheme, lanthanum is loaded on the biochar prepared by taking wetland plants as raw materials through a hydrothermal method, so that the lanthanum-modified biochar substrate capable of efficiently removing phosphorus is obtained. The method of synthesizing the hydrothermal method in one step is adopted, the process is simple, the cost is low, and the yield is high.
The hydrothermal lanthanum biochar prepared by the technical scheme disclosed by the invention provides adsorption phosphorus removal sites for lanthanum, also provides a slow-release carbon source for the denitrification process of microorganisms, can realize synchronous enhanced nitrogen and phosphorus removal, and is simple and efficient, and high in yield.
According to the hydrothermal method adopted by the technical scheme, lanthanum can be combined to biochar in a hydrated lanthanum oxide form, and the method is efficient and stable.
The raw material proportion used in the technical scheme of the method can maximize the utilization rate of wetland plants and the loading effect of lanthanum, and obtains the optimized phosphorus removal effect.
According to the technical scheme, the most common plants in the wetland are used as raw materials for preparing the biochar, so that the resource recycling of wetland plants is promoted, and the problem of blockage of the artificial wetland caused by waste plants in winter is solved.
The lanthanum used in the technical scheme disclosed by the invention has strong affinity with phosphorus, stable binding capacity and low price, and can be easily complexed with phosphate by virtue of the surface functional groups of the biochar after being bound with the biochar, and the pollution of the generated phosphate deposition to the wetland bottom layer is avoided.
According to the technical scheme, the wetland system constructed by taking the hydrothermal lanthanum biochar as the improved substrate has high phosphorus removal efficiency.
Advantages of additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to limit the disclosure.
FIG. 1 is a comparison of the phosphorus adsorption capacity of the present disclosure and a conventional filler quartz sand;
FIG. 2 is a graph showing the variation of the retention time of the conventional filler quartz sand according to the hydraulic force and the phosphorus adsorption amount.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The embodiments and features of the embodiments in the present disclosure may be combined with each other without conflict.
Example 1
Discloses a preparation method of a lanthanum-modified constructed wetland biochar substrate by a hydrothermal method, which comprises the following steps:
(1) the method comprises the steps of airing, cleaning and drying stems of wetland plant reed, cutting the stems into small pieces of 1-2cm, placing the small pieces in a hydrothermal reaction kettle, and adding ammonia water with the mass ratio of 1:0.3, lanthanum with the mass ratio of 1:0.1 and pure water with the mass ratio of 1: 10.
(2) And (2) carrying out hydrothermal carbonization treatment on the reaction system in the step (1) in an oxygen-limited environment, wherein the reaction temperature is 240 ℃, the reaction time is 10 hours, filtering and separating precipitates after the reaction is finished, washing the precipitates with deionized water, and drying the precipitates at the temperature of 75 ℃ to constant weight to obtain the lanthanum-loaded wetland plant biochar.
Example 2
Discloses a preparation method of a lanthanum-modified constructed wetland biochar substrate by a hydrothermal method, which comprises the following steps:
(1) the method comprises the steps of airing, cleaning and drying stems of wetland plant reed, cutting the stems into small pieces of 1-2cm, placing the small pieces in a hydrothermal reaction kettle, and adding ammonia water with the mass ratio of 1:0.6, lanthanum with the mass ratio of 1:0.1 and pure water with the mass ratio of 1: 10.
(2) And (2) carrying out hydrothermal carbonization treatment on the reaction system in the step (1) in an oxygen-limited environment, wherein the reaction temperature is 240 ℃, the reaction time is 10 hours, filtering and separating precipitates after the reaction is finished, washing the precipitates with deionized water, and drying the precipitates at the temperature of 75 ℃ to constant weight to obtain the lanthanum-loaded wetland plant biochar.
Example 3
Discloses a preparation method of a lanthanum-modified constructed wetland biochar substrate by a hydrothermal method, which comprises the following steps:
(1) the method comprises the steps of airing, cleaning and drying stems of wetland plant reed, cutting the stems into small pieces of 1-2cm, placing the small pieces in a hydrothermal reaction kettle, and adding ammonia water with the mass ratio of 1:1, lanthanum with the mass ratio of 1:0.1 and pure water with the mass ratio of 1: 10.
(2) And (2) carrying out hydrothermal carbonization treatment on the reaction system in the step (1) in an oxygen-limited environment, wherein the reaction temperature is 240 ℃, the reaction time is 10 hours, filtering and separating precipitates after the reaction is finished, washing the precipitates with deionized water, and drying the precipitates at the temperature of 75 ℃ to constant weight to obtain the lanthanum-loaded wetland plant biochar.
Example 4
Discloses a lanthanum-modified constructed wetland biochar substrate prepared by a hydrothermal method, which is characterized in that lanthanum-modified biochar is obtained by adopting the method of any one of the implementation examples 1-3, and the lanthanum-modified biochar is mixed with a conventional substrate in a proportion of 1: the proportion of 4 is used by doping. The lanthanum modified biochar matrix is adopted to construct an artificial wetland.
Application experiments
The hydrothermal lanthanum biochar substrate prepared in the example 4 is used for enhanced phosphorus removal of the artificial wetland:
two groups of cylindrical artificial wetland models are constructed by organic glass materials, the diameter is 20cm, the height is 50cm, and the bottom of each model is ensured to be stable by a fixed tray with the diameter of 35 cm. The wetland substrate is lanthanum modified biochar substrate and quartz sand. The wetland plants are reed, and the planting area is 16 plants per square meter. The water inlet of the system is artificially prepared phosphorus-containing sewage (1-5mg/L), and the water inlet modes are intermittent water inlet.
As shown, fig. 1 is a comparison of the present disclosure with phosphorus removal capacity at different feed water concentrations of phosphorus, with adsorption capacity expressed as adsorption capacity.
FIG. 2 shows that the phosphorus concentration of the feed water is 5mg/L compared with the phosphorus adsorption amount of the conventional filler quartz sand under different hydraulic retention time.
The above description is only a preferred embodiment of the present disclosure and is not intended to limit the present disclosure, and various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Although the present disclosure has been described with reference to specific embodiments, it should be understood that the scope of the present disclosure is not limited thereto, and those skilled in the art will appreciate that various modifications and changes can be made without departing from the spirit and scope of the present disclosure.
Claims (8)
1. A preparation method of a lanthanum-modified constructed wetland biochar substrate by a hydrothermal method is characterized by comprising the following steps:
drying, cleaning, drying and chopping the straws of the wetland plants, putting the straws into a hydrothermal reaction kettle, and adding a mixed aqueous solution of ammonia water and lanthanum chloride; the ammonia water not only adds surface nitrogen functional groups for the biochar, but also provides an alkaline environment, so that lanthanum is tightly complexed with the biochar in a hydrated oxidation state;
carrying out hydrothermal carbonization treatment on the hydrothermal reaction kettle in an oxygen-limited environment; the reaction temperature is 200 ℃ and 300 ℃, and the reaction time is 10-20 hours;
and after the hydrothermal carbonization treatment reaction is finished, filtering and separating precipitates, washing the precipitates with deionized water, and drying the precipitates to constant weight to obtain the hydrothermal lanthanum modified biochar, namely the hydrothermal lanthanum biochar for short, which is used as a substrate of the artificial wetland.
2. The preparation method of the hydrothermal lanthanum-modified artificial wetland biochar substrate as claimed in claim 1, wherein the mass ratio of wetland plants to lanthanum is 1:0.05-0.1, the mass ratio of wetland plants to ammonia water is 1:0.3-1, and the mass ratio of wetland plants to pure water is 1: 10-20.
3. The preparation method of the hydrothermal lanthanum-modified artificial wetland biochar substrate as claimed in claim 1, wherein the wetland plants are selected from one or a combination of reed, calamus or typha.
4. The preparation method of the hydrothermal lanthanum-modified constructed wetland biochar substrate as claimed in claim 1, wherein the stems of wetland plants are air-dried, cleaned, dried and cut into small pieces of 1-2 cm.
5. The preparation method of the hydrothermal lanthanum-modified constructed wetland biochar substrate as claimed in claim 1, wherein the biochar substrate is washed with deionized water and dried at 75 ℃ to constant weight.
6. A lanthanum-modified constructed wetland biochar substrate prepared by a hydrothermal method, which is characterized by being obtained by the method of any one of claims 1 to 5.
7. A method for strengthening phosphorus removal of artificial wetlands is characterized in that the hydrothermal lanthanum-modified artificial wetland biochar substrate in claim 6 is mixed with other wetland substrates in a ratio of 1: 4.
8. The method for enhancing phosphorus removal in artificial wetlands of claim 7, wherein other wetland substrates are one of quartz sand, zeolite or gravel.
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| CN110180498A (en) * | 2019-05-23 | 2019-08-30 | 江苏省农业科学院 | Carry the preparation method and application of lanthanum magnetism hydro-thermal charcoal adsorbent |
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