CN111644158A - Carbon-based adsorbent for removing phosphate in solution - Google Patents
Carbon-based adsorbent for removing phosphate in solution Download PDFInfo
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- CN111644158A CN111644158A CN202010425089.1A CN202010425089A CN111644158A CN 111644158 A CN111644158 A CN 111644158A CN 202010425089 A CN202010425089 A CN 202010425089A CN 111644158 A CN111644158 A CN 111644158A
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- 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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- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
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- 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
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- 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
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- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/18—Semi-solid fertilisers, e.g. foams or gels
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- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/40—Fertilisers incorporated into a matrix
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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
- C02F2101/105—Phosphorus compounds
Abstract
The invention discloses a carbon-based adsorbent for removing phosphate in a water body, which is prepared by the following method: (1) uniformly mixing the biomass raw material and the mineral material according to the weight ratio of 1-5:1, feeding the mixture into a carbonization furnace for carbonization, and crushing the carbonized product to obtain mineral material modified biochar; (2) performing dilute alkali treatment on the mineral material modified charcoal; (3) adding agar 1kg, starch 0.5-1kg and carbon-based adsorbent 1-3kg into deionized water 40-60L, ultrasonically dispersing, heating to 50-60 deg.C, stirring, mixing, and naturally cooling to obtain gel. The invention has good effect on adsorbing and removing the excessive phosphate in the water body, can adsorb the phosphate in the water body, reduce the concentration of phosphorus in the water body, relieve the water body pollution such as agricultural non-point source pollution, eutrophication and the like, is easy to separate from the water body, and can be used as a soil conditioner.
Description
Technical Field
The invention relates to the technical field of water treatment agent production, in particular to a carbon-based adsorbent for removing phosphate in a solution.
Background
Eutrophication (eutrophy) refers to the phenomenon of water pollution caused by excessive content of nutrient salts such as N, P in water. The essence of the method is that the species distribution of the water ecosystem is unbalanced and a single species grows excessively due to the unbalanced input and output of nutritive salt, so that the flow of substances and energy of the system is damaged, and the whole water ecosystem gradually goes to death.
Excessive phosphate can cause eutrophication of water bodies, which can adversely affect biological health and the environment. The excess phosphorus in the water is mainly derived from fertilizers, agricultural wastes and municipal sewage. The data show that over the past 15 years the phosphate content of surface water has increased 25-fold, with 60% of the phosphate entering the water in the united states coming from municipal sewage. The main source of phosphate in municipal sewage is detergents, which, in addition to causing eutrophication of water, also cause a large amount of foam to be produced by many waters. The excessive phosphorus in the water body comes from external industrial wastewater and domestic sewage on one hand. On the other hand, the method has the endogenous effect that the bottom mud in the water body releases phosphate under the reduction state, so that the content of phosphorus is increased, particularly in eutrophic lakes caused by nitrate, the system is rapidly deteriorated due to more complicated discharge of municipal sewage, and the problem can not be solved even if the phosphate addition is stopped.
Prevention and control of eutrophication is the most complex and difficult problem in water pollution treatment. This is because: firstly, the complexity of pollution sources, nitrogen and phosphorus nutrient substances causing water eutrophication, not only have natural sources, but also have artificial sources; both exogenous and endogenous. This presents difficulties in controlling the source of the pollution; ② high difficulty in removing nutrient substances. Biological phosphorus removal is a relatively economic phosphorus removal method, but the requirement on environmental conditions is relatively high to ensure that the stable effluent phosphorus meets the requirement of 0.5mg/L standard. The high-valence metal salt commonly used in the chemical method has relatively high cost and is easy to cause secondary pollution. After chemical phosphorus removal, the treated substances are difficult to separate from the water body, and the separated products have high treatment cost.
Biochar is a highly stable solid substance produced by pyrolysis and carbonization of biomass under limited oxygen conditions. The raw materials for preparing the biochar have wide sources, such as agricultural wastes, bamboo wood, fruit shells and the like. As a novel adsorption material, the molecular weight is fine and porous, the surface area is large, the adsorption capacity is super strong, and the application in the fields of environmental protection, soil geology, atmospheric science and the like is wide. It is commonly used in water purification, air deodorization, humidity regulation and preservation, and room health care in daily life.
Disclosure of Invention
The invention aims to provide a carbon-based adsorbent for removing phosphate in a solution, which has a good effect of adsorbing and removing excessive phosphate in a water body, can adsorb phosphate in the water body, reduce the concentration of phosphorus in the water body, relieve water body pollution such as agricultural non-point source pollution and eutrophication, is easy to separate from the water body, and can be used as a soil conditioner.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a carbon-based adsorbent for removing phosphate in a water body is prepared by the following method:
(1) uniformly mixing the biomass raw material and the mineral material according to the weight ratio of 1-5:1, feeding the mixture into a carbonization furnace for carbonization, and crushing the carbonized product to obtain mineral material modified biochar;
(2) performing dilute alkali treatment on the mineral material modified biochar, then washing the biochar for 3 to 5 times by using deionized water, and performing centrifugal drying to obtain a primary carbon-based adsorbent;
(3) adding 1kg of agar, 0.5-1kg of starch and 1-3kg of primary carbon-based adsorbent into 40-60L of deionized water, ultrasonically dispersing for 20-30 minutes, heating to 50-60 ℃, stirring and mixing for 30-60 minutes, naturally cooling to obtain gel, and cutting the gel into round or square small blocks to obtain the finished product.
Calcite is a novel natural adsorption material appearing in recent years and comprises the chemical component of CaCO3The crystal form belongs to a trigonal carbonate mineral, has strong fixing capacity on phosphate, and has the characteristics of no toxicity, no harm, low price, large specific surface area and good adsorption performance. The invention gives full play to the excellent characteristics of the biochar and uses the biochar to prepare the high-efficiency phosphorus adsorbent.
In order to solve the problem of recycling of the adsorbent, the invention further disperses the mineral material modified biochar into a specific porous gel carrier, the single porous gel carrier (agar starch base) has certain phosphate adsorption capacity, the porous pore channel composition and the pore diameter of the porous gel carrier and the mineral material modified biochar are different, a certain complementary and rich porous structure can be formed, the mineral material modified biochar is combined with the porous gel carrier, not only can the phosphate adsorption capacity be improved, but also the adsorbent can be made into block-shaped gel, the use and the recovery are convenient, meanwhile, the porous gel carrier is made of natural substances, the environment is protected and pollution-free, the mineral material modified biochar is environment-friendly and pollution-free and can also be used as a soil conditioner, the adsorbent adsorbing phosphate and nitrogen salt after the recovery can be directly used as a green soil conditioner for improving the lean soil, effectively recycling the nutrients. Low cost, easy obtaining, safe environment, convenient application, easy popularization and obvious environmental and economic benefits.
Preferably, the biomass raw material is selected from one or more of rice hull, mao bamboo, hickory shell, peanut shell and bagasse.
Preferably, the mineral material is calcite.
Preferably, the carbonization treatment is carried out at a temperature of 500-700 ℃ for 2-3 hours.
Preferably, the mineral material modified biochar is obtained by crushing to 80-150 meshes.
Preferably, the dilute alkali treatment is to immerse the mineral material modified biochar in dilute alkali liquor, heat the mineral material modified biochar to 35-45 ℃, and stir the mineral material modified biochar for 1-2 hours at 50-80 rpm. Through the treatment of specific dilute alkali liquor, the pore channels in the mineral material modified biochar can be further perfected and accessed, so that the phosphate adsorption capacity of the biochar is improved.
Preferably, the composition of the dilute alkali solution is as follows: 5-10% of sodium hydroxide, 10-15% of sodium carbonate and the balance of water.
Preferably, the biomass feedstock is blended with the mineral material in a weight ratio of 4.2: 1.
A method for using carbon-based adsorbent for removing phosphate in water body includes loading carbon-based adsorbent in blocks into multiple mesh bags, putting the mesh bags into water body to be treated, taking out the mesh bags after 24 hr, taking out the carbon-based adsorbent in blocks, and applying it as fertilizer to barren soil.
The invention has the beneficial effects that: the method has good effect on adsorbing and removing excessive phosphate in the water body, can adsorb the phosphate in the water body, reduce the concentration of phosphorus in the water body, relieve agricultural non-point source pollution, eutrophication and other water body pollution, is easy to separate from the water body, and can be used as a soil conditioner.
Drawings
FIG. 1 is a Fourier Transform Infrared (FTIR) spectrum of various materials;
(a) calcite; (b) rice hulls; (c) rice hull biochar (carbonization condition is 700 ℃, 2.3 h); (d) calcite modified rice hull biochar (the carbonization condition is 700 ℃, 2.3h, the ratio of the rice hull to the calcite is 4.2: 1); (e) calcite modified rice hull biochar 1 after phosphate adsorption (carbonization conditions are 700 ℃, 2.3h, rice hull: calcite is 4.2: 1; adsorption experiment conditions are that the initial concentration of phosphate is 10mg/L, the addition amount of an adsorbent is 2.5g, the pH of a reaction system is 5.6; and the reaction time is 24 h); (f) and (3) adsorbing phosphate to obtain calcite modified rice hull biochar 2 (the carbonization condition is 700 ℃, the time is 2.3h, the rice hull is calcite 4.2:1, the adsorption experiment condition is that the initial concentration of phosphate is 95mg/L, the addition amount of an adsorbent is 0.24g, the pH of a reaction system is 5.4, and the reaction time is 11.75 h).
FIG. 2 is an X-ray spectrogram (XRD) of various materials;
(a) rice hulls; (b) calcite; (c) rice hull biochar (carbonization condition is 700 ℃, 2.3 h); (d) calcite modified rice hull biochar (the carbonization condition is 700 ℃, 2.3h, the ratio of the rice hull to the calcite is 4.2: 1); (e) calcite modified rice hull biochar 1 after phosphate adsorption (carbonization conditions are 700 ℃, 2.3h, rice hull: calcite is 4.2: 1; adsorption experiment conditions are that the initial concentration of phosphate is 10mg/L, the addition amount of an adsorbent is 2.5g, the pH of a reaction system is 5.6; and the reaction time is 24 h); (f) and (3) adsorbing phosphate to obtain calcite modified rice hull biochar 2 (the carbonization condition is 700 ℃, the time is 2.3h, the rice hull is calcite 4.2:1, the adsorption experiment condition is that the initial concentration of phosphate is 95mg/L, the addition amount of an adsorbent is 0.24g, the pH of a reaction system is 5.4, and the reaction time is 11.75 h).
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) of different materials;
RH: rice hulls; BRH: rice hull biochar (carbonization condition is 700 ℃, 2.3 h); BRH-C: calcite modified rice hull biochar (the carbonization condition is 700 ℃, 2.3h, the ratio of the rice hull to the calcite is 4.2: 1); calcite: calcite; BRH + C-Opt 1: calcite modified rice hull biochar 1 after phosphate adsorption (carbonization conditions are 700 ℃, 2.3h, rice hull: calcite is 4.2: 1; adsorption experiment conditions are that the initial concentration of phosphate is 10mg/L, the addition amount of an adsorbent is 2.5g, the pH of a reaction system is 5.6; and the reaction time is 24 h); BRH + C-Opt 2: and (3) adsorbing phosphate to obtain calcite modified rice hull biochar 2 (the carbonization condition is 700 ℃, the time is 2.3h, the rice hull is calcite 4.2:1, the adsorption experiment condition is that the initial concentration of phosphate is 95mg/L, the addition amount of an adsorbent is 0.24g, the pH of a reaction system is 5.4, and the reaction time is 11.75 h).
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a carbon-based adsorbent for removing phosphate in a water body is prepared by the following method:
(1) uniformly mixing a biomass raw material (rice hull) and calcite according to a weight ratio of 1:1, sending the mixture into a carbonization furnace for carbonization under the condition that the temperature is 500 ℃ for 3 hours, and crushing the mixture to 80-150 meshes to obtain the calcite modified biochar.
(2) Carrying out dilute alkali treatment on the calcite modified biochar, then washing the calcite modified biochar for 3 times by using deionized water, and centrifugally drying the calcite modified biochar to obtain a primary carbon-based adsorbent; the dilute alkali treatment is to immerse calcite modified biochar in dilute alkali liquor, heat to 35 ℃, and stir at 50 revolutions per minute for 2 hours; the dilute alkali solution comprises the following components: 5% of sodium hydroxide, 15% of sodium carbonate and the balance of water.
(3) Adding 1kg of agar, 0.5kg of starch and 1kg of primary carbon-based adsorbent into 40L of deionized water, ultrasonically dispersing for 20 minutes, heating to 50 ℃, stirring and mixing for 60 minutes, naturally cooling to obtain gel, and cutting the gel into round small blocks (such as 1cm in diameter and 0.5cm in thickness) to obtain the final product.
Example 2:
a carbon-based adsorbent for removing phosphate in a water body is prepared by the following method:
(1) uniformly mixing a biomass raw material (moso bamboo) and calcite according to a weight ratio of 5:1, sending the mixture into a carbonization furnace for carbonization under the condition that the temperature is 700 ℃ and the time is 2 hours, and crushing the mixture to 80-150 meshes to obtain the calcite modified biochar.
(2) Carrying out dilute alkali treatment on the calcite modified biochar, then washing the calcite modified biochar for 5 times by using deionized water, and centrifugally drying the calcite modified biochar to obtain a primary carbon-based adsorbent; the dilute alkali treatment is to immerse calcite modified biochar in dilute alkali liquor, heat to 45 ℃, stir at 80 r/min for 1 hour; the dilute alkali solution comprises the following components: 10% of sodium hydroxide, 10% of sodium carbonate and the balance of water.
(3) Adding 1kg of agar, 1kg of starch and 3kg of primary carbon-based adsorbent into 60L of deionized water, ultrasonically dispersing for 30 minutes, heating to 60 ℃, stirring and mixing for 30 minutes, naturally cooling to obtain gel, and cutting the gel into square small blocks (such as 1cm in length, width and height) to obtain the finished product.
Example 3:
a carbon-based adsorbent for removing phosphate in a water body is prepared by the following method:
(1) uniformly mixing a biomass raw material (hickory nut shells) and calcite according to a weight ratio of 4.2:1, sending the mixture into a carbonization furnace for carbonization under the conditions of 600 ℃ and 2.5 hours, and crushing the mixture to 80-150 meshes to obtain the calcite modified biochar.
(2) Carrying out dilute alkali treatment on the calcite modified biochar, then washing the calcite modified biochar for 4 times by using deionized water, and centrifugally drying the calcite modified biochar to obtain a primary carbon-based adsorbent; the dilute alkali treatment is to immerse calcite modified biochar in dilute alkali liquor, heat to 40 ℃, and stir at 60 revolutions per minute for 1.5 hours; the dilute alkali solution comprises the following components: 8% of sodium hydroxide, 12% of sodium carbonate and the balance of water.
(3) Adding 1kg of agar, 0.8kg of starch and 2kg of primary carbon-based adsorbent into 50L of deionized water, ultrasonically dispersing for 25 minutes, heating to 55 ℃, stirring and mixing for 40 minutes, naturally cooling to obtain gel, and cutting the gel into square small blocks (such as 1cm in length, width and height) to obtain the finished product.
Experimental studies were carried out on rice hulls:
scheme 1
Taking a mixture of rice hulls and calcite according to a ratio of 1:1 as a raw material, heating the mixture in a carbonization furnace at a carbonization temperature of 350-550 ℃ for 1-2.5 hours to evaporate free moisture contained in the mixture and decompose hemicellulose, cellulose and lignin, simultaneously generating a large amount of pyrolysis products, finishing the reaction at 550 ℃, basically carbonizing the raw material, cooling the raw material to room temperature, taking out the raw material from a discharge port, and crushing the raw material to obtain calcite-rice hull biochar, namely calcite modified biochar.
Scheme 2
The method comprises the steps of taking a mixture of rice hulls and calcite according to a ratio of 3:1 as a raw material, heating the mixture in a carbonization furnace at a carbonization temperature of 500-700 ℃ for 1-4 hours to evaporate free moisture contained in the mixture and decompose hemicellulose, cellulose and lignin, generating a large amount of pyrolysis products at the same time, finishing the reaction at 700 ℃, basically carbonizing the raw material, cooling the raw material to room temperature, taking the raw material out of a discharge port, and crushing the raw material to obtain calcite-moso bamboo biochar, namely calcite modified biochar.
Scheme 3
Taking a mixture of rice hulls and calcite according to a ratio of 5:1 as a raw material, heating the mixture in a carbonization furnace for 2.5-4h at a carbonization temperature of 500-700 ℃ to evaporate free moisture contained in the mixture and decompose hemicellulose, cellulose and lignin, and simultaneously generating a large amount of pyrolysis products, finishing the reaction at 700 ℃, basically carbonizing the raw material, cooling the raw material to room temperature, taking out the raw material from a discharge port, and crushing the raw material to obtain calcite-rice hull biochar, namely calcite modified biochar.
Adsorption tests were performed using calcite-modified biochar. Taking calcite modified biochar obtained by mixing rice hulls and calcite according to different proportions under the conditions of serial carbonization temperature and carbonization time, respectively carrying out adsorption experiments on phosphate solutions with initial concentrations of 10mg/L, wherein the dosage of the calcite modified biochar is 0.25g, the pH value of a solution system is 5.6, the reaction time is 24h, after the experiments are finished, detecting the concentration of phosphate in the solution, and calculating the removal rate of phosphate. The results are shown in Table 1. The carbonization process conditions are optimized by adopting a response surface method, the optimal conditions are that the mixing ratio of the rice hulls to the calcite is 4.2:1, the carbonization temperature is 700 ℃, the carbonization time is 2.3h, and the removal rate of phosphate reaches 87.3 percent under the conditions.
TABLE 1 adsorption removal rate of calcite-modified biochar on phosphate in solution
Generally lignocellulosic biomass is rich in hydroxyl groups and Fourier transform infrared spectroscopy (graph)1) Middle 3335cm-1The strong peak corresponds to the stretching of O-H, which shows that hydroxyl exists on the surface of the rice hull (b), but the rice hull biochar (c) and calcite modified rice hull biochar (d) after high-temperature carbonization at 700 ℃ completely disappear. Similarly, there was a stretch of aliphatic C-H in the hulls (2919 cm)-1) And disappears in (c) and (d), indicating that the aliphatic is converted to an aromatic structure during the high temperature carbonization process and the cellulose is completely degraded. The samples of the calcite (a) and the calcite modified rice hull biochar (d) are 711, 871 and 1393cm-1As evidenced by characteristic peaks near (v). SiO is also present in the rice husk (b) and the calcite modified rice husk biochar (d)2(452 and 1031cm-1Nearby). The calcite modified rice hull biochar sample (f) is 560cm-1The nearby special peak indicates that PO appears on the surface of the sample after the adsorption reaction4 3-. SiO of samples (e) and (f) after adsorption2Peak is 449cm-1To 437cm-1And 441cm-1The movement indicates that the phosphate may interact (e.g. electrostatically) with the silicate present in the base sample (d).
The results of the X-ray spectrogram (XRD) analysis are shown in FIG. 2. As can be seen, the calcite sample (b) is relatively pure and has distinct characteristic peaks. SiO is present in the rice husk (a) and the rice husk biochar (c)2And exists in an amorphous form. The thermodynamically stable pure calcite peak appears in the calcite-modified rice hull biochar (d), indicating that the calcite-modification treatment increases the opportunity for phosphate adsorption removal by the rice hull biochar. The XRD spectrograms of the calcite modified rice hull biochar samples (e and f) after adsorbing the phosphate are almost the same as that of the original sample (d) before adsorbing, and a calcium phosphate precipitation peak is not generated, which indicates that the calcite modified rice hull biochar does not adsorb and remove the phosphate through a mechanism of precipitation phosphorus removal. This is because calcium contained in calcite-modified rice hull biochar cannot be released into solution to precipitate with phosphate because of the extremely low solubility of calcite.
The chemical compositions of calcite-modified rice hull biochar (BRH + C-Opt1 and BRH + C-Opt2) after adsorbing phosphate are researched by adopting an X-ray photoelectron energy spectrum (XPS), and the result is shown in FIG. 3. The peaks of O1s (532.1eV for metal carbonate) and C1 s (284 eV) of each sample are identified in the mapCorresponding to C-C/C-H,288eV for carbonate), Si 2p peak (103.1eV for SiO2) Si 2s peak (154eV for SiO)2) Ca 2s peak (439eV corresponds to CaCO)3). After adsorbing phosphate, the P2 s peak (191.1eV) corresponding to phosphate in the calcite-modified rice hull biochar samples (BRH + C-Opt1 and BRH + C-Opt2) can be clearly identified, which further verifies the chemisorption of phosphate by calcite-modified rice hull biochar under different optimization conditions.
Calcite-modified biochar was prepared according to the optimal conditions in scheme 4, and dilute alkali treatment and gelation were performed according to step (2) of examples 1-3, comparing the effect on the adsorption removal rate of phosphate before and after dilute alkali treatment.
And (3) experimental setting: carrying out an adsorption experiment by using a phosphate solution with the initial concentration of 10mg/L, wherein the dosage of an adsorbent is 0.25g, the pH of a solution system is 5.6, the reaction time is 24h, and after the experiment is finished, detecting the concentration of phosphate in the solution and calculating the removal rate of phosphate. The results are shown in Table 2.
TABLE 2 adsorption removal of phosphate from solution
| Serial number | Phosphate removal rate (%) of the adsorbent after the dilute alkali treatment |
| Example 1 | 87.6％ |
| Example 2 | 88.2％ |
| Example 3 | 87.8％ |
。
Scheme 6
Preparing calcite modified biochar according to the optimal conditions in the scheme 4, and comparing the influence on the adsorption removal rate of phosphate after adding or not adding the gel of the calcite modified biochar.
Adding 1g of agar, 1g of starch and 2g of calcite modified biochar into 50mL of deionized water, performing ultrasonic dispersion for 25 minutes, heating to 55 ℃, stirring and mixing for 40 minutes, naturally cooling to obtain gel, cutting the gel into square small blocks (the length, the width and the height are 0.5cm), and adding no calcite modified biochar in a comparative example, wherein the test setting is as follows: carrying out an adsorption experiment by using a phosphate solution with the initial concentration of 10mg/L, setting 30 times of repeated use of the adsorbent, wherein the pH value of a solution system is 5.6, the reaction time is 24h, detecting the concentration of phosphate in the solution after the experiment is finished, and calculating the removal rate of phosphate, wherein the average removal rate of a test group is 92.1%, and the removal rate of a control group is 37.8%.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (9)
1. The carbon-based adsorbent for removing phosphate in water is characterized by being prepared by the following method:
(1) uniformly mixing the biomass raw material and the mineral material according to the weight ratio of 1-5:1, feeding the mixture into a carbonization furnace for carbonization, and crushing the carbonized product to obtain mineral material modified biochar;
(2) performing dilute alkali treatment on the mineral material modified biochar, then washing the biochar for 3 to 5 times by using deionized water, and performing centrifugal drying to obtain a primary carbon-based adsorbent;
(3) adding 1kg of agar, 0.5-1kg of starch and 1-3kg of primary carbon-based adsorbent into 40-60L of deionized water, ultrasonically dispersing for 20-30 minutes, heating to 50-60 ℃, stirring and mixing for 30-60 minutes, naturally cooling to obtain gel, and cutting the gel into round or square small blocks to obtain the finished product.
2. The carbon-based adsorbent for removing phosphate from a body of water according to claim 1, wherein: the biomass raw material is selected from one or more of rice hull, moso bamboo, hickory shell, peanut shell and bagasse.
3. The carbon-based adsorbent for removing phosphate from a body of water according to claim 1, wherein: the mineral material is calcite.
4. The carbon-based adsorbent for removing phosphate from a body of water according to claim 1, wherein: the carbonization treatment condition is 500-700 ℃ and the time is 2-3 hours.
5. The carbon-based adsorbent for removing phosphate from a body of water according to claim 1, wherein: pulverizing to 80-150 mesh to obtain mineral material modified biochar.
6. The carbon-based adsorbent for removing phosphate from a body of water according to claim 1, wherein: the dilute alkali treatment is to immerse the mineral material modified biochar in dilute alkali liquor, heat to 35-45 ℃, stir at 50-80 rpm for 1-2 hours.
7. The carbon-based adsorbent for removing phosphate from a body of water according to claim 6, wherein: the dilute alkali solution comprises the following components: 5-10% of sodium hydroxide, 10-15% of sodium carbonate and the balance of water.
8. The carbon-based adsorbent for removing phosphate from a body of water according to claim 1 or 2, wherein: the biomass raw material and the mineral material are uniformly mixed according to the weight ratio of 4.2: 1.
9. The use of a carbon-based sorbent for the removal of phosphate from a body of water according to claim 1, wherein: filling the blocky carbon-based adsorbent into a plurality of mesh bags, putting the mesh bags into the water body to be treated, taking out the mesh bags after 24 hours, taking out the blocky carbon-based adsorbent, and applying the blocky carbon-based adsorbent serving as a soil conditioner to the barren soil.
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