CN114713190A - Sewage phosphorus removal agent and preparation method thereof - Google Patents
Sewage phosphorus removal agent and preparation method thereof Download PDFInfo
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- CN114713190A CN114713190A CN202210403041.XA CN202210403041A CN114713190A CN 114713190 A CN114713190 A CN 114713190A CN 202210403041 A CN202210403041 A CN 202210403041A CN 114713190 A CN114713190 A CN 114713190A
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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
- B01J20/04—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
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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
- B01J20/04—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
- B01J20/045—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 containing sulfur, e.g. sulfates, thiosulfates, gypsum
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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
- B01J20/20—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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- 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
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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
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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
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract
The invention discloses a sewage phosphorus removing agent and a preparation method thereof. Cleaning plant materials with deionized water, oven drying, pyrolyzing for 1 hr by oxygen-limiting temperature-rising carbonization, and grinding into powder for use. And (3) preserving the natural gypsum in a 120 ℃ oven for 2h, naturally cooling, grinding and sieving by a 100-mesh sieve. And (3) uniformly mixing 30-60% of gypsum and 70-40% of biochar to obtain the phosphorus removing agent. According to the content of total phosphorus in the sewage, a phosphorus removing agent with the mass of 0.1-0.5% of the water body is put into the sewage, and a good phosphorus removing effect can be achieved after the reaction is carried out for 3 days. The raw materials are cheap and easy to obtain, and the modification processing technology is simple. The phosphorus removal agent has the advantages of small usage amount, no need of special treatment and low operation cost. After treatment, the inorganic phosphate crystallized on the surface of the phosphorus removing agent is insoluble in water, and cannot cause secondary pollution to a water body. The device is suitable for treating phosphorus-containing sewage with different concentrations, has a good purification effect on phosphorus-containing sewage with different pH values, and is less influenced by water temperature.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a preparation method of a sewage phosphorus removal agent and the sewage phosphorus removal agent prepared by the preparation method.
Background
With the development of phosphorus chemical industry such as agriculture, detergents and the like, the over-standard phosphorus content in natural water is more and more common. Phosphorus is the most important factor for the growth of planktonic algae and is one of the main causes of eutrophication pollution of water bodies. The control of the phosphorus concentration of the water body is a key technology for solving the problem of water body eutrophication.
The water body dephosphorization technology can be divided into: chemical method, biological method, adsorption method, and crystallization method. The chemical phosphorus removal method is to add chemical agents into the sewage to generate insoluble salts, and the insoluble salts are separated from the water after forming flocculating constituents, so that phosphorus in the sewage is removed. The chemical method has complex process and high cost, and is generally used for industrial sewage treatment. Biological phosphorus removal is generally to convert phosphorus in a water body into polyphosphate by utilizing the biological action of bacteria, has low cost, slow effect and poor effect, and is generally combined with a chemical phosphorus removal method for use. The adsorption and phosphorus removal is realized by utilizing the bonding effect of active groups of the adsorption material and phosphorus, so that the phosphorus is enriched and the phosphorus removal effect is further achieved. The adsorption method has wide application range, but is influenced by the saturated adsorption quantity of the material and the pH value of the water body, and the adsorbed phosphorus is easily released to the water body to cause secondary pollution. The crystallization method is to generate insoluble calcium hydroxy phosphate or struvite crystal from phosphorus in water body, thereby achieving the separation effect. The process is influenced by the pH, the ratio of the amounts of substances between the reactants, the type of seed and the reaction time.
In order to overcome the defects of the prior art, a preparation method and an application method of a water body phosphorus removal agent using biochar and gypsum as raw materials are provided. The phosphorus removal agent has the advantages of low raw material cost, simple preparation process and high phosphorus removal efficiency, and has better purification effect on phosphorus-containing sewage with different concentrations.
Disclosure of Invention
Based on the analysis, the sewage phosphorus removal agent has low raw material cost, simple preparation process and high phosphorus removal efficiency, and has better purification effect on phosphorus-containing sewage with different concentrations, and is urgently needed in the industry at present.
The invention is realized by the following means:
a sewage dephosphorizing agent, comprising:
30-60% of modified gypsum; and
40-70% of charcoal;
wherein, the biochar is prepared from plant raw materials, and the plant raw materials comprise one or more of rice straw, corn straw, soybean straw and rice hull.
Further, the sewage phosphorus removal agent comprises:
45% of modified gypsum; and
55 percent of biochar.
The invention also discloses a method for preparing the sewage dephosphorizing agent, which comprises the following steps:
preparing biochar;
preparing modified gypsum; and
and mixing the biochar with the modified gypsum to obtain the sewage dephosphorizing agent.
Further, the biochar is prepared by the following method:
cleaning the plant materials with deionized water, and oven drying at 50 deg.C for 12 hr;
carrying out pyrolysis for 1h by adopting an oxygen-limited heating carbonization method;
naturally cooling, and grinding to 35-100 meshes to obtain the biochar for later use.
Further, the plant materials include, but are not limited to: one or more of rice straw, corn straw, soybean straw and rice hull.
Further, the limited oxygen heating carbonization pyrolysis comprises:
heating to 500-800 ℃ in a nitrogen-filled tube furnace at a heating rate of 10-20 ℃/min.
Further, the modified gypsum is prepared by the following method:
the natural gypsum is put in an oven with the temperature of 120 ℃ for heat preservation for 2 hours, and is ground after natural cooling and then is sieved by a 100-mesh sieve for standby.
The invention also discloses a sewage dephosphorizing agent prepared by any one of the preparation methods.
The invention also discloses an application of any one of the sewage dephosphorizing agents in sewage treatment.
Further, the application includes:
selecting a water body with pH of 5-9 and total phosphorus concentration of 0.1-200mg/L, adding a phosphorus removal agent with the mass of 0.1-0.5% of the water body into the sewage according to the content of the total phosphorus in the sewage, and reacting at the temperature of 0-40 ℃ for 3 days, wherein the phosphorus removal rate is 90-98%.
The invention has the beneficial effects that:
(1) the raw materials are cheap and easy to obtain, and the modification processing technology is simple.
(2) The phosphorus removal agent has the advantages of small usage amount, no need of special treatment and low operation cost.
(3) After treatment, the inorganic phosphate crystallized on the surface of the phosphorus removing agent is insoluble in water, and cannot cause secondary pollution to a water body.
(4) The device is suitable for treating phosphorus-containing sewage with different concentrations, has a good purification effect on phosphorus-containing sewage with different pH values, and is less influenced by water temperature. According to the implementation effect of a laboratory, the dephosphorization effect after treatment basically reaches more than 90 percent.
(5) The coarse grain phosphorus removal agent is convenient to recover, and the phosphorus can be recycled.
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.
The gypsum used in the following examples was purchased from Dow Cologne Chemicals, Inc., analytically pure, CaSO4·2H2The content of O is more than or equal to 99 percent, and the rice and corn straws are collected from farmlands.
Example 1
A preparation method of a sewage dephosphorization treating agent comprises the following steps:
(1) preparing modified gypsum: placing natural gypsum in an oven at 120 ℃, preserving heat for 2h, naturally cooling, grinding, and sieving with a 100-mesh sieve;
(2) preparing biochar: washing collected rice straw with deionized water, drying at 50 ℃ for 12h, heating to 700 ℃ in a vacuum tube furnace at the heating rate of 10 ℃/min, introducing nitrogen at the ventilation rate of 1L/min in the whole process, pyrolyzing for 1h to obtain biochar, naturally cooling, and grinding to 50 meshes;
(3) mixing the following raw materials in percentage by mass: 1, uniformly mixing the modified gypsum and the biochar to obtain the phosphorus removing agent.
1g of the phosphorus removal agent prepared in the example 1 is added into 1L of sewage with the total phosphorus concentration of 1mg/L, pH-6.5, and the mixture is fully and uniformly mixed, so that the total phosphorus concentration of the sewage reaches 0.1mg/L after 3 days at the temperature of 25 ℃, and the phosphorus removal rate reaches 90%.
Example 2
A preparation method of a sewage dephosphorization treating agent comprises the following steps:
(1) preparing modified gypsum: placing natural gypsum in an oven at 120 ℃, preserving heat for 2h, naturally cooling, grinding, and sieving with a 100-mesh sieve;
(2) preparing biochar: and cleaning the collected soybean straws with deionized water, and drying for 12 hours at 50 ℃. Heating to 600 ℃ in a vacuum tube furnace at the heating rate of 15 ℃/min, introducing nitrogen at the ventilation rate of 1L/min in the whole process, pyrolyzing for 1h to prepare biochar, naturally cooling, and grinding to 35 meshes;
(3) and (3) uniformly mixing the modified gypsum and the biochar in a mass ratio of 3:7 to obtain the phosphorus removing agent.
1g of the phosphorus removal agent prepared in the example 2 is added into 1L of sewage with the total phosphorus concentration of 5mg/L, pH-7, and the mixture is fully and uniformly mixed, so that the total phosphorus concentration of the sewage reaches 0.4mg/L after 3 days at the constant temperature of 15 ℃, and the phosphorus removal rate reaches 92%.
Example 3
A preparation method of a sewage dephosphorization treating agent comprises the following steps:
(1) preparing modified gypsum: placing natural gypsum in an oven at 120 ℃, preserving heat for 2h, naturally cooling, grinding, and sieving with a 100-mesh sieve;
(2) preparing the biochar: and cleaning the collected corn straws by deionized water, and drying for 12 hours at 50 ℃. Heating to 650 ℃ in a vacuum tube furnace at the heating rate of 12 ℃/min, introducing nitrogen at the ventilation rate of 1L/min in the whole process, pyrolyzing for 1h to prepare biochar, naturally cooling, and grinding to 45 meshes;
(3) and uniformly mixing the modified gypsum and the biochar in a mass ratio of 4:6 to obtain the phosphorus removing agent.
5g of the phosphorus removal agent prepared in the embodiment 3 is added into 1L of sewage with the total phosphorus concentration of 50mg/L, pH-8.0, the mixture is fully and uniformly mixed, the total phosphorus concentration of the sewage reaches 0.9mg/L after 3 days at the constant temperature of 25 ℃, and the phosphorus removal rate reaches 98.2%.
Example 4
The preparation method of the sewage dephosphorization treating agent comprises the following steps:
(1) preparing modified gypsum: placing natural gypsum in an oven at 120 ℃, preserving heat for 2h, naturally cooling, grinding, and sieving with a 100-mesh sieve;
(2) preparing biochar: and cleaning the collected corn straws by deionized water, and drying for 12 hours at 50 ℃. Heating to 800 deg.C in vacuum tube furnace at a heating rate of 20 deg.C/min, introducing nitrogen at a ventilation rate of 1L/min, pyrolyzing for 1 hr to obtain charcoal, naturally cooling, and grinding to 100 mesh;
(3) and uniformly mixing the modified gypsum and the biochar in a mass ratio of 45:55 to obtain the phosphorus removing agent.
5g of the phosphorus removal agent prepared in the example 5 is added into 1L of sewage with the total phosphorus concentration of 150mg/L, pH-9.0, the mixture is fully and uniformly mixed, the total phosphorus concentration of the sewage reaches 5.2mg/L after 3 days at the constant temperature of 40 ℃, and the phosphorus removal rate reaches 96.2%.
Comparative example 1
A preparation method of a sewage dephosphorization treating agent comprises the following steps:
(1) preparing modified gypsum: placing natural gypsum in an oven at 120 ℃, preserving heat for 2h, naturally cooling, grinding, and sieving with a 100-mesh sieve;
(2) preparing biochar: and (3) washing the collected rice straws with deionized water, and drying for 12 hours at 50 ℃. Heating to 700 deg.C in a vacuum tube furnace at a heating rate of 10 deg.C/min, introducing nitrogen gas at a ventilation rate of 1L/min, pyrolyzing for 1 hr to obtain charcoal, naturally cooling, and grinding to 35-100 mesh;
(3) mixing 1: 1, uniformly mixing the modified gypsum and the biochar to obtain the phosphorus removing agent.
1g of the phosphorus removal agent prepared in the comparative example 1 is added into 1L of sewage with the total phosphorus concentration of 25mg/L, pH-6.5, the mixture is fully and uniformly mixed, the total phosphorus concentration of the sewage reaches 11.9mg/L after 3 days at the constant temperature of 25 ℃, and the phosphorus removal rate reaches 52.3%.
Compared with the example 1, the total phosphorus concentration of the comparative example 1 is increased, and the phosphorus removal dosage is unchanged, so that the phosphorus removal rate is low, and the dosage or the pH value of the phosphorus removal agent can be properly increased, so that the phosphorus removal efficiency is improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A sewage phosphorus removal agent, comprising:
30-60% of modified gypsum; and
40-70% of charcoal;
wherein, the biochar is prepared from plant raw materials, and the plant raw materials comprise one or more of rice straw, corn straw, soybean straw and rice hull.
2. The sewage phosphorus removal agent of claim 1, wherein:
45% of modified gypsum; and
55 percent of biochar.
3. A method of preparing the sewage phosphorous removal agent of claim 1 or 2, comprising:
preparing biochar;
preparing modified gypsum; and
and mixing the biochar with the modified gypsum to obtain the sewage dephosphorizing agent.
4. The production method according to claim 3, wherein:
the biochar is prepared by the following method:
cleaning the plant materials with deionized water, and drying at 50 deg.C for 12 hr;
carrying out pyrolysis for 1h by adopting an oxygen-limited heating carbonization method;
naturally cooling, and grinding to 35-100 meshes to obtain the biochar for later use.
5. The production method according to claim 4, wherein:
the plant raw material comprises one or more of rice straw, corn straw, soybean straw and rice hull.
6. The production method according to claim 4, wherein:
the limited oxygen heating carbonization pyrolysis method comprises the following steps:
heating to 500-800 ℃ in a nitrogen-filled tube furnace at a heating rate of 10-20 ℃/min.
7. The production method according to claim 3, wherein:
the modified gypsum is prepared by the following method:
the natural gypsum is put in an oven with the temperature of 120 ℃ for heat preservation for 2 hours, and is ground after natural cooling and then is sieved by a 100-mesh sieve for standby.
8. A sewage dephosphorizing agent prepared by the preparation method according to any one of claims 3-7.
9. The application of the sewage dephosphorizing agent of any one of claims 1, 2 and 8 in sewage treatment.
10. The use according to claim 9, comprising:
selecting a water body with pH of 5-9 and total phosphorus concentration of 0.1-200mg/L, adding a phosphorus removal agent with the mass of 0.1-0.5% of the water body into the sewage according to the content of the total phosphorus in the sewage, and reacting at the temperature of 0-40 ℃ for 3 days, wherein the phosphorus removal rate is 90-98%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210403041.XA CN114713190A (en) | 2022-04-18 | 2022-04-18 | Sewage phosphorus removal agent and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116173901A (en) * | 2022-12-22 | 2023-05-30 | 济南大学 | Porous biochar prepared from red gypsum and crop straw and application of porous biochar in heavy metal adsorption |
| CN117303529A (en) * | 2023-11-13 | 2023-12-29 | 厦门汇科天工净水材料有限公司 | Preparation method of dephosphorizing agent for sewage treatment |
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