CN111039376A - Composite efficient phosphorus removal agent applied to sewage treatment field and preparation method thereof - Google Patents
Composite efficient phosphorus removal agent applied to sewage treatment field and preparation method thereof Download PDFInfo
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- CN111039376A CN111039376A CN201911419835.XA CN201911419835A CN111039376A CN 111039376 A CN111039376 A CN 111039376A CN 201911419835 A CN201911419835 A CN 201911419835A CN 111039376 A CN111039376 A CN 111039376A
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- sulfate
- sulfuric acid
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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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 composite efficient phosphorus removal agent applied to the field of sewage treatment and a preparation method thereof, wherein the preparation method comprises the following steps: step one, producing polymeric ferric sulfate: the polyferric sulfate is prepared by adopting a two-step method, sulfuric acid and ferrous sulfate heptahydrate are used for reaction, strong oxidant oxygen is added to oxidize Fe2+, and a polyferric sulfate liquid product can be obtained after full reaction. Step two, producing aluminum sulfate: the aluminum hydroxide reacts with sulfuric acid to obtain aluminum sulfate, the aluminum hydroxide is white powder, and the sulfuric acid is industrial waste acid. Corresponding to the sulfuric acid used for producing polymeric ferric sulfate. And step three, compounding aluminum sulfate and polymeric ferric sulfate. The raw materials such as ferrous sulfate, sulfuric acid and the like used in the invention are wastes in chemical production, so that the production cost can be saved and the resource utilization of the wastes can be realized.
Description
Technical Field
The invention relates to a composite efficient phosphorus removal agent applied to the field of sewage treatment and a preparation method thereof.
Background
The widely adopted phosphorus removal methods are mainly biological phosphorus removal and chemical phosphorus removal. At present, sewage treatment plants mainly adopt a biological method to treat nitrogen and phosphorus in water, but most of town sewage in China belongs to a low carbon source and is difficult to meet the requirement of biological nitrogen removal and biological phosphorus removal on the carbon source at the same time, so that the content of phosphorus in effluent water cannot reach the national specified standard, and in order to meet the increasingly strict national sewage discharge standard, more and more sewage treatment plants adopt a chemical auxiliary phosphorus removal method to further remove phosphorus.
The chemical phosphorus removal efficiency is higher than that of biological phosphorus removal, the discharge standard that the total phosphorus in effluent is less than 1mg/L can be achieved under the general condition, the method is not greatly influenced by seasons, is stable and reliable, does not generate secondary pollution caused by secondary release of phosphorus in the sludge treatment process, and has the advantages of strong impact resistance, low capital construction cost and the like. At present, in the aspect of phosphorus removal, common coagulants mainly comprise calcium salt, aluminum salt and iron salt, and inorganic and organic composite flocculants which are developed rapidly at present.
The poly-ferric sulfate and the ferric sulfate are formed by inserting hydroxyl into a network structure of ferric sulfate molecular clusters to form OH-For the multinuclear complex ion of bridging formation, gather iron and compare with water purification agent such as traditional ferric trichloride, ferric sulfate, outstanding characteristics are: the flocculant has excellent coagulation performance, wide pH value range suitable for water, strong capacity of removing BOD, COD and heavy metal ions in water, effects of decoloring, deodorizing, dehydrating, deoiling and the like, little residual iron ions, small rancidity during use and the like. However, the metal salt phosphorus removal agent has poor phosphorus removal effect, is easy to cause new pollution, and has a narrow application range, while the natural adsorbent has a huge specific surface area, but can only remove phosphorus through physical adsorption without modification, and has poor effect, while the flocculant generally plays an auxiliary role in the phosphorus removal process, and when the phosphorus removal agent is used alone, the application range of the phosphorus removal agent to the pH of the sewage is narrow. Therefore, the research on novel efficient complexing agents is one of the main directions of the research.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a composite efficient phosphorus removal agent applied to the field of sewage treatment.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention discloses a composite efficient phosphorus removal agent applied to the field of sewage treatment, which comprises 8-10% of polymeric ferric sulfate, 5-10% of aluminum sulfate and the balance of water by mass percent.
On the other hand, the invention discloses a preparation method of a composite efficient phosphorus removal agent applied to the field of sewage treatment, which comprises the following steps:
step one, producing polymeric ferric sulfate: the polyferric sulfate is prepared by adopting a two-step method, sulfuric acid and ferrous sulfate heptahydrate are used for reaction, strong oxidant oxygen is added to oxidize Fe2+, and a polyferric sulfate liquid product can be obtained after full reaction.
Step two, producing aluminum sulfate: the aluminum hydroxide reacts with sulfuric acid to obtain aluminum sulfate, the aluminum hydroxide is white powder, and the sulfuric acid is industrial waste acid. Corresponding to the sulfuric acid used for producing polymeric ferric sulfate.
Step three, compounding aluminum sulfate and polymeric ferric sulfate:
adding the finished product of the polymeric ferric sulfate in the step one into a stirring kettle for producing liquid polymeric aluminum sulfate in the step two according to a proportion, and adding a certain amount of water according to a specific proportion to obtain the polymeric ferric sulfate; the components by mass percentage are 8 to 10 percent of polymeric ferric sulfate, 5 to 10 percent of aluminum sulfate and the balance of water.
Preferably, the step one specifically comprises:
(1) adding a certain amount of water into the dissolving tank in proportion, slowly injecting the metered 98% concentrated sulfuric acid while stirring, simultaneously weighing a certain amount of ferrous sulfate heptahydrate, pouring the ferrous sulfate heptahydrate into the dissolving tank, and uniformly mixing;
(2) pumping the mixed solution of ferrous sulfate heptahydrate and sulfuric acid into a reaction kettle through a pipeline for reaction, adding a catalyst sodium nitrite, and then sealing the reaction kettle;
(3) the polymeric ferric sulfate is prepared by hydrolytic polymerization, and the raw materials have the following proportions: ferrous sulfate heptahydrate: 98% sulfuric acid: water: sodium nitrite: liquid oxygen 142.86: 12.0: 46.8: 1: 3.86.
(4) and after the reaction is finished, turning off an oxygen switch, releasing pressure, discharging the ferric sulfate solution in the reaction kettle into a finished product pool, and curing for 10-14 hours to form a dark brown polymeric ferric sulfate water purifying agent product.
Preferably, in the step (2), the mass fraction of the sodium nitrite solution is 20%.
Preferably, in the step (2), after the reaction kettle is sealed, the oxygen switch is opened, gaseous oxygen with the purity of 99.5% is continuously introduced through a pipeline for reaction, the reaction pressure is 0.35MPa, the reaction is exothermic, and the temperature is controlled to be 55-65 ℃ in the reaction process.
Preferably, the second step specifically comprises:
(1) firstly, adding a certain amount of water into a stirring kettle according to a certain proportion, then adding a certain amount of sulfuric acid into the stirring kettle through a pipeline pump, then adding stoichiometric or slightly excessive aluminum hydroxide, stirring to fully react, and finally adding a certain amount of water to obtain a finished product of liquid aluminum sulfate;
(2) the aluminum sulfate is prepared by reacting aluminum hydroxide with sulfuric acid, and the raw materials comprise: aluminum hydroxide: 98% sulfuric acid: water 1: 3: 6.
the invention has the following beneficial effects:
(1) high phosphorus removal efficiency
The polymeric sulfuric acid consists of single components, has single function, large dosage and poor dephosphorization effect, and is difficult to discharge after reaching the standard after being applied to municipal sewage treatment. Al (OH) produced by dissolving aluminum sulfate in water2+、Al(OH)2+And AlO2The mononuclear complexes form a series of polynuclear complexes Aln (OH) m (3n-m) (n) by collision condensation>1, m is less than or equal to 3n), the polynuclear complex has higher positive charge and specific surface area, can quickly adsorb impurities in a water body, and assists polymeric ferric sulfate to improve the dephosphorization efficiency.
(2) Less dosage and less sludge production
Compared with the single polymeric ferric sulfate phosphate removing agent, the composite efficient phosphate removing agent has less dosage, and under the same dosage, the production amount of sludge is greatly reduced, thereby reducing the subsequent sludge treatment cost of a sewage treatment plant.
(3) Low investment and cost
Compared with other phosphorus removal agents, the composite efficient phosphorus removal agent disclosed by the invention has the advantages that the types of related agents are few, the production cost of the agents is reduced, the phosphorus removal effect is improved, and the application prospect is wide.
(4) Meanwhile, can remove other pollutants
According to practical application, the composite efficient phosphorus removal agent disclosed by the invention can achieve a good phosphorus removal effect through flocculation precipitation and adsorption under the synergistic effect of the two agents, has a good effect on removing ammonia nitrogen and COD, and greatly improves the water quality standard of the effluent of a sewage treatment plant.
(5) Has low corrosion to equipment and convenient use
In the production process of the composite efficient phosphorus removal medicament, the adopted production process has small corrosivity, and the service life of related equipment is greatly prolonged. The invention relates to a composite efficient phosphorus removal agent for sewage treatment, wherein the product is in a liquid finished product state, can be directly used in use, does not need to be diluted, and is convenient for actual operation and use, so that the labor intensity of workers is reduced.
(6) Realizes the resource utilization of the waste
The raw materials such as ferrous sulfate, sulfuric acid and the like used in the invention are wastes in chemical production, so that the production cost can be saved, the resource utilization of the wastes can be realized, and the method conforms to the relevant national environmental protection policies.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a process flow diagram for the production of liquid polymeric ferric sulfate;
FIG. 2 is a process flow diagram for aluminum sulfate production.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
The composite efficient phosphorus removing agent comprises polymeric ferric sulfate and aluminum sulfate, wherein the polymeric ferric sulfate and the aluminum sulfate comprise 10% of polymeric ferric sulfate, 5-10% of aluminum sulfate and the balance of water by mass percent, an aluminum sulfate finished product and the polymeric ferric sulfate are prepared into the composite efficient phosphorus removing agent, and if the concentration of phosphorus is too high, the adding amount of the polymeric ferric sulfate and the aluminum sulfate can be properly increased.
The master batch of the composite efficient phosphorus removal agent is polymeric ferric sulfate, which has proved to have good effect on the aspect of sewage phosphorus removal, but with the increasing national standard for sewage discharge, a single water treatment agent cannot meet the current national standard, so after a large amount of experimental exploration, the composite efficient phosphorus removal agent is produced, and the polymeric ferric sulfate and aluminum sulfate are compounded to prepare a novel composite efficient phosphorus removal agent to meet the requirements of the current sewage treatment market.
The composite efficient phosphorus removal agent is added into the effluent of the biological aeration tank, and enters a secondary sedimentation tank for sedimentation after hydraulic stirring, and compared with the single phosphorus removal agent of polymeric ferric sulfate, the phosphorus removal rate is improved by 10-20%, and the composite efficient phosphorus removal agent has good phosphorus removal effect on municipal sewage with different concentrations. The composite efficient phosphorus removal agent provided by the embodiment of the invention is used for removing phosphorus, flocculating, precipitating, deodorizing and sterilizing in domestic sewage and industrial wastewater treatment, and has the characteristics of fast flocculating precipitation, good effects of settling mud dragging water and phosphorus removal and the like. The composite efficient phosphorus removal agent disclosed by the embodiment of the invention has no corrosion to equipment, and can be directly added with drugs in water without influence on microorganisms.
The production method comprises the following specific production steps:
step one, producing polymeric ferric sulfate: the polymeric ferric sulfate is prepared by a two-step method. Reacting sulfuric acid with ferrous sulfate heptahydrate, adding strong oxidant oxygen to react Fe2+The oxidation speed of ferrous sulfate by oxygen is slow, so as to improve Fe2+And adding a small amount of catalyst sodium nitrite into the mixture for full reaction to obtain a polymeric ferric sulfate liquid product. As shown in fig. 1.
(1) Adding a certain amount of water into the dissolving tank in proportion, slowly injecting the metered 98% concentrated sulfuric acid while stirring, simultaneously weighing a certain amount of ferrous sulfate heptahydrate (FeSO4 & 7H2O), pouring into the dissolving tank, and uniformly mixing. The dissolving tank is semi-closed, only the feed inlet is opened, the pressure is normal, the temperature in the dissolving tank is about 30 ℃ after the materials are mixed, and the feed inlet is 1.2m multiplied by 0.7 m.
(2) The mixed solution of ferrous sulfate heptahydrate and sulfuric acid was pumped into a reaction vessel (the inner diameter of the charging port was 0.08m) through a pipe to carry out the reaction. For increasing Fe2+The dissolved sodium nitrite (NaNO) with the concentration of 20 percent is pumped by a centrifugal pump2) Adding the solution (catalyst) into a reaction kettle; then the reaction kettle is sealed, an oxygen switch is opened, oxygen (gaseous oxygen with the purity of 99.5%) is continuously introduced through a pipeline to carry out reaction, the reaction pressure is 0.35MPa (the pressure is regulated by the oxygen), the reaction is exothermic reaction, and the temperature is controlled to be about 60 ℃ in the reaction process.
(3) The polymeric ferric sulfate is prepared through hydrolytic polymerization, and the production time of each batch of products is 4 hours. The proportion of each raw material is as follows: ferrous sulfate heptahydrate: 98% sulfuric acid: water: sodium nitrite: liquid oxygen 142.86: 12.0: 46.8: 1: 3.86.
(4) after the reaction is finished, turning off an oxygen switch, releasing pressure, discharging the ferric sulfate solution in the reaction kettle into a finished product pool, and curing for 12 hours to form a dark brown polymeric ferric sulfate water purifying agent product.
(5) The feeding is pumped by a pipeline, and the reaction kettle is in a fully closed state in the feeding process, so that sulfuric acid mist is not generated; the reaction kettle is also totally closed in the reaction process, and the process has no emission of sulfuric acid mist. A small amount of nitrogen oxide is discharged in the pressure relief and discharging process.
(6) The low-temperature liquid oxygen is sent to a storage place by a liquid oxygen professional supplier and is filled into a liquid oxygen storage tank in a liquid state; liquid oxygen is conveyed to the air temperature type high-pressure vaporizer through the self pressure of the tank body, and the vaporizer vaporizes low-temperature liquid oxygen by absorbing the heat of air and ensures that the temperature of gas discharged from the vaporizer is not lower than 5 ℃ of the ambient temperature; after vaporization, the pressure is adjusted to the pressure required by the reaction kettle through a pressure regulating valve, and then the vapor is conveyed into the reaction kettle through a pipeline.
(7) And (3) the trace acid gas volatilized in the dissolving tank and the reaction kettle in the polymerization ferric sulfate reaction process enters the bottom of the water washing absorption tower through an acid gas discharge pipeline through a draught fan, and the waste gas is discharged up to the standard after the acid gas is sequentially in reverse contact with the process water from bottom to top. The wastewater obtained after absorption treatment is returned to the sedimentation tank as process water and recycled by a process water pump. Polyferric sulfate is a set of waste gas treatment system (waste acid recycling that produces in the polyferric sulfate production process carries out secondary production).
FIG. 2 shows, step two, production of aluminum sulfate:
(1) the invention relates to a method for preparing aluminum sulfate from ferric aluminum hydroxide, which utilizes the reaction of aluminum hydroxide and sulfuric acid to obtain the aluminum sulfate, wherein the aluminum hydroxide is white powder as a raw material, and the sulfuric acid is industrial waste acid. Corresponding to the sulfuric acid used for producing polymeric ferric sulfate.
(2) Firstly, a certain amount of water is added into a stirring kettle according to a certain proportion, then a certain amount of sulfuric acid is added into the stirring kettle through a pipeline pump, then stoichiometric or slightly excessive aluminum hydroxide is added, the mixture is stirred to fully react, and finally a certain amount of water is added to obtain the finished product of liquid aluminum sulfate.
(3) The aluminum sulfate is prepared by the reaction of aluminum hydroxide and sulfuric acid, and the production time of each batch of products is 1 h. The proportion of each raw material is as follows: aluminum hydroxide: 98% sulfuric acid: water 1: 3: 6.
(4) the amount of the sulfuric acid added later is controlled by a flowmeter, the amount of the aluminum hydroxide added is quantitative and known, full reaction can be well guaranteed, and the whole reaction process does not need heating.
(5) The stirring kettle is semi-closed, not only plays an effective heat preservation role to promote the reaction, but also avoids the harm to operators and reaction equipment caused by overlarge pressure in the reaction process.
(6) Because the raw material of ferric aluminum hydroxide is simple and the production process is simple, the cost can be effectively saved, and the aluminum sulfate and the polymeric ferric sulfate are compounded
And (3) proportionally adding the finished product of the polymeric ferric sulfate in the step one into a stirring kettle for producing liquid polymeric aluminum sulfate in the step two, and adding a certain amount of water according to a specific proportion to prepare the composite efficient phosphorus removal agent. The content of each component is 10 percent of polymeric ferric sulfate, 5 to 10 percent of aluminum sulfate and the balance of water according to mass percentage. The proportion of each medicament in the invention can be properly adjusted according to different water quality requirements.
The specific application examples of the product of the invention are as follows:
the composite efficient phosphorus removal agent is applied and produced in sewage treatment plants in Ningxia and surrounding areas and obtains good effect, and the following examples are applied to the sewage treatment plants:
the total phosphorus content before treatment is 5.23mg/L, the maximum removal rate can reach 92%, and the content is reduced to 0.4 mg/L.
The following table shows the specific experimental results:
the product is applied to a sewage treatment plant of a bioengineering company in Ningxia to carry out dephosphorization, and has a very obvious effect, the total phosphorus content before treatment is 12.4mg/L, and the maximum removal rate is 89%.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The composite efficient phosphorus removal agent applied to the field of sewage treatment is characterized by comprising 8-10% of polymeric ferric sulfate, 5-10% of aluminum sulfate and the balance of water by mass percent.
2. The preparation method of the composite efficient phosphorus removal agent applied to the sewage treatment field of claim 1 is characterized by comprising the following steps:
step one, producing polymeric ferric sulfate: the polymeric ferric sulfate is prepared by adopting a two-step method, sulfuric acid and ferrous sulfate heptahydrate are used for reaction, and strong oxidant oxygen is added to react Fe2+Oxidizing and fully reacting to obtain a polymeric ferric sulfate liquid product.
Step two, producing aluminum sulfate: the aluminum hydroxide reacts with sulfuric acid to obtain aluminum sulfate, the aluminum hydroxide is white powder, and the sulfuric acid is industrial waste acid.
Step three, compounding aluminum sulfate and polymeric ferric sulfate:
adding the finished product of the polymeric ferric sulfate in the step one into a stirring kettle for producing liquid polymeric aluminum sulfate in the step two according to a proportion, and adding a certain amount of water according to a specific proportion to obtain the polymeric ferric sulfate; the components by mass percentage are 8 to 10 percent of polymeric ferric sulfate, 5 to 10 percent of aluminum sulfate and the balance of water.
3. The preparation method of the composite efficient phosphorus removal agent applied to the field of sewage treatment as claimed in claim 2, wherein the first step specifically comprises:
(1) adding a certain amount of water into the dissolving tank in proportion, slowly injecting the metered 98% concentrated sulfuric acid while stirring, simultaneously weighing a certain amount of ferrous sulfate heptahydrate, pouring the ferrous sulfate heptahydrate into the dissolving tank, and uniformly mixing;
(2) pumping the mixed solution of ferrous sulfate heptahydrate and sulfuric acid into a reaction kettle through a pipeline for reaction, adding a catalyst sodium nitrite, and then sealing the reaction kettle;
(3) the polymeric ferric sulfate is prepared by hydrolytic polymerization, and the raw materials have the following proportions: ferrous sulfate heptahydrate: 98% sulfuric acid: water: sodium nitrite: liquid oxygen 142.86: 12.0: 46.8: 1: 3.86.
(4) and after the reaction is finished, turning off an oxygen switch, releasing pressure, discharging the ferric sulfate solution in the reaction kettle into a finished product pool, and curing for 10-14 hours to form a dark brown polymeric ferric sulfate water purifying agent product.
4. The method for preparing the composite efficient phosphorus removal agent applied to the field of sewage treatment according to claim 3, wherein in the step (2), the mass fraction of the sodium nitrite solution is 20%.
5. The method for preparing the composite efficient phosphorus removal agent applied to the field of sewage treatment according to claim 3, wherein in the step (2), after the reaction kettle is sealed, an oxygen switch is opened, gaseous oxygen with the purity of 99.5% is continuously introduced through a pipeline for reaction, the reaction pressure is 0.35MPa, the reaction is an exothermic reaction, and the temperature is controlled to be 55-65 ℃ in the reaction process.
6. The preparation method of the composite efficient phosphorus removal agent applied to the field of sewage treatment according to claim 2, wherein the second step specifically comprises:
(1) firstly, adding a certain amount of water into a stirring kettle according to a certain proportion, then adding a certain amount of sulfuric acid into the stirring kettle through a pipeline pump, then adding stoichiometric or slightly excessive aluminum hydroxide, stirring to fully react, and finally adding a certain amount of water to obtain a finished product of liquid aluminum sulfate;
(2) the aluminum sulfate is prepared by reacting aluminum hydroxide with sulfuric acid, and the raw materials comprise: aluminum hydroxide: 98% sulfuric acid: water 1: 3: 6.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112299541A (en) * | 2020-10-24 | 2021-02-02 | 山东普尼奥水处理有限公司 | Efficient composite phosphorus removal agent suitable for capacity-expansion sewage treatment system and preparation method thereof |
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| CN110054267A (en) * | 2019-03-21 | 2019-07-26 | 山东益源环保科技有限公司 | A kind of high efficiency composition dephosphorization agent and its application method in municipal wastewater deep phosphorous removal |
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| CN112299541A (en) * | 2020-10-24 | 2021-02-02 | 山东普尼奥水处理有限公司 | Efficient composite phosphorus removal agent suitable for capacity-expansion sewage treatment system and preparation method thereof |
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