CN110577269A - Composite reagent for removing manganese and ammonia nitrogen in wastewater and application method thereof - Google Patents
Composite reagent for removing manganese and ammonia nitrogen in wastewater and application method thereof Download PDFInfo
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- CN110577269A CN110577269A CN201910977996.4A CN201910977996A CN110577269A CN 110577269 A CN110577269 A CN 110577269A CN 201910977996 A CN201910977996 A CN 201910977996A CN 110577269 A CN110577269 A CN 110577269A
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- wastewater
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
- C02F1/64—Heavy metal compounds of iron or manganese
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
the invention provides a composite medicament for removing manganese and ammonia nitrogen in wastewater and an application method thereof, belonging to the technical field of water treatment in environmental protection. The composite medicament comprises the following components in percentage by mass: 30-45% of colloidal particle carrier, 10-20% of ion settling agent and 30-50% of ammonia removing agent; when the composite agent is used for removing manganese and ammonia nitrogen in wastewater, the composite agent is used together with an organic polymer and a coagulant aid. The composite medicament is prepared by compounding the colloidal particle carrier, the ion settling agent and the ammonia removal agent, has a very good effect of removing manganese and ammonia nitrogen, can reduce the concentration of manganese in water to below 1mg/L and the concentration of ammonia nitrogen to below 5mg/L, and has the removal rate of manganese and ammonia nitrogen in wastewater respectively reaching 99.9 percent and more than 99 percent.
Description
Technical Field
The invention belongs to the technical field of water treatment in environmental protection, and particularly relates to a composite reagent for removing manganese and ammonia nitrogen in wastewater and an application method thereof.
background
Manganese is an important metal element, has wide application range in industry and large demand, is an important raw material in metallurgical industry, and is also used in aspects of nonferrous metal, chemical industry, medicine, food, analysis, scientific research and the like.
The ammonia nitrogen refers to nitrogen existing in the form of free ammonia (NH3) and ammonium ions (NH4+), excessive ammonia nitrogen in water can not only cause eutrophication of water bodies, but also can be converted into nitrite under certain conditions, if the water is drunk for a long time, the nitrite in the water is combined with protein to form nitrosamine, which is a strong carcinogenic substance and is extremely unfavorable for human health.
at present, the treatment of manganese and ammonia nitrogen in wastewater is mainly divided treatment in engineering application, namely firstly removing manganese in wastewater by a traditional precipitation method, a flocculation sedimentation method, an electrolysis method and other methods, and then removing ammonia nitrogen in water by air stripping, air flotation and a microbiological method. The conventional precipitation method removes metal ions from wastewater by reacting hydroxide, carbonic acid compound or sulfide with metal ions in wastewater to generate precipitate having low solubility. The method can achieve the manganese ion concentration of effluent less than 5mg/L by treating the acidic manganese-containing wastewater by a traditional chemical precipitation method after adjusting the pH value, but has the problems of longer process, harsh treatment conditions, higher cost, more waste residues, introduction of secondary pollution, limited treatment capacity and the like. The flocculation precipitation method is to destabilize and aggregate small particles and colloidal particles which are difficult to precipitate in the wastewater into large particles by using a coagulant to precipitate, thereby realizing the removal of heavy metal ions. Research shows that the electrolytic manganese wastewater is treated by lime-polyaluminium chloride, the pH is controlled to be 8.5-10.0, and the manganese in the wastewater can be reduced to 0.2mg/L from 397mg/L when the electrolytic manganese wastewater is added with the mass concentration of 50 mg/L. However, the flocculation sedimentation method requires an increase in pH to facilitate sedimentation, and as a result, the pH of the effluent is high, and the like. The electrolytic method for treating the wastewater with low manganese ion concentration has the advantages of high removal rate, no secondary pollution, low energy consumption, recoverable precipitated heavy metal, strong adaptability to the change of the water quality of the wastewater, short reaction time, large energy consumption when treating a large amount of wastewater, large consumption of electrode metal and unsuitability for high-concentration wastewater. The three-dimensional electrolysis technology in the iron scrap micro-electrolysis method is suitable for the hydraulic engineering in high manganese areas, but the micro-electrolysis method is usually used for treating wastewater under an acidic condition, so that the dissolved iron scrap is large in quantity or the treatment effect is not obvious.
the method has the advantages that ammonia nitrogen is removed by a stripping method, namely, gas is introduced into water, gas and liquid are in full contact with each other, free ammonia dissolved in the water passes through a gas-liquid interface and is transferred to a gas phase, so that the aim of removing the ammonia nitrogen is fulfilled, the energy consumption and the cost of the method are relatively high, a special collecting and treating device needs to be constructed for ammonia recovery liquid, and the technology has the advantages that high-concentration ammonia nitrogen wastewater is treated, and the limitation is large. The ammonia nitrogen is removed by an air floatation method, ammonia nitrogen and free ammonia are adsorbed by adding an air floatation agent, a large amount of micro bubbles are generated in water, a three-phase mixture of water, gas and removed substances is formed, and after micro bubbles are promoted to be adhered to the removed ammonia nitrogen under the combined action of various forces such as interfacial tension, bubble rising buoyancy, hydrostatic pressure difference and the like, the micro bubbles float to the water surface because the density of an adhesive body is smaller than that of the water, so that the ammonia nitrogen in the water is separated and removed, the selection of the air floatation agent for removing the ammonia nitrogen by the air floatation method is particularly important. The method for removing ammonia nitrogen by a microbiological method is widely applied to the core process of domestic sewage and most of ammonia nitrogen wastewater treatment, the nitrifying bacteria and the denitrifying bacteria in the activated sludge are utilized to convert the ammonia nitrogen into nitrate radicals, and then the nitrate radicals are denitrified into nitrogen, so that the removal effect is achieved, but a large amount of residual sludge is generated after treatment, and the secondary pollution is large.
Disclosure of Invention
The invention provides a composite medicament for removing manganese and ammonia nitrogen in wastewater and an application method thereof, and solves the technical problems of secondary pollution and harsh treatment conditions easily caused by sewage treatment in the prior art.
In order to achieve the purpose, the technical solution of the invention is as follows:
A composite medicament for removing manganese and ammonia nitrogen in wastewater comprises the following components in percentage by mass: 30-45% of colloidal particle carrier, 10-20% of ion settling agent and 30-50% of ammonia removing agent.
Preferably, the colloidal particle carrier is one or two of ferric chloride, ferrous sulfide, ferrous chloride, aluminum sulfate, magnesium sulfate and magnesium chloride.
Preferably, the ionic settling agent is one or two of sodium sulfide, calcium sulfide, aluminum oxide, calcium oxide and magnesium sulfide.
Preferably, the ammonia remover is one of calcium hypochlorite, sodium hypochlorite and potassium hypochlorite.
the invention provides application of a composite medicament for removing manganese and ammonia nitrogen in wastewater, wherein the composite medicament is used together with an organic polymer and a coagulant aid.
Preferably, the organic polymer is one of dithiocarbamate, trimercaptotriazine trisodium salt, and methyl ethyl sulfide.
Preferably, the coagulant aid is one of polyacrylamide, sodium polyacrylate and polyaluminium chloride.
The invention provides an application method of a composite reagent for removing manganese and ammonia nitrogen in wastewater, which comprises the following steps:
S1: taking the colloidal particle carrier and the ion settling agent according to a certain proportion, uniformly stirring at a rotating speed of 30rpm, slowly adding the ammonia removing agent, fully stirring at a rotating speed of 50rpm, and standing for 20-40min to obtain a composite medicament;
S2: adding the composite medicament prepared in the step S1 into wastewater with the manganese concentration and the ammonia nitrogen concentration of 100-1500 mg/L and 200-500 mg/L respectively, controlling the mass ratio of the composite medicament to the wastewater to be 1:50-1:150, controlling the pH to be 7.8-9.5, and uniformly stirring at the rotating speed of 50rpm for 20-30min to separate out colloid particles;
s3: adding an organic polymer and a coagulant aid into the wastewater in the step S2, wherein the mass ratio of the organic polymer to the wastewater is 1:100-1:2000, the mass ratio of the coagulant aid to the wastewater is 1:500-1:1000, slowly stirring the mixture for 30min at 20rpm, standing the mixture to separate sludge from water, and the effluent can reach the primary standard of the comprehensive wastewater discharge standard (GB 2-1996).
The action principle of the invention is as follows:
Colloidal particle carrier: the iron, aluminum and magnesium chloride salts can form a complex colloid of hydroxide in a slightly alkaline environment, have good complexing and loading effects on the precipitation of manganese hydroxide, and chloride ions have an oxidation promoting effect in the ammonia removal process, so that although certain hydroxide ions are consumed, the pH is adjusted after the compound agent is added, and the reaction balance can not obviously move.
An ion settling agent: different from common alkaline demanganization, the method selects alkaline sodium salt, calcium salt, magnesium salt and the like, hydrolyzes in water to be alkaline, and reacts with manganese ions in water to generate manganese hydroxide precipitate.
Ammonia removing agent: the main principle is breakpoint chlorination, ammonia nitrogen in water is oxidized, chloramine is generated firstly, then nitrogen is generated, and the ammonia nitrogen is removed;
Organic polymer (b): the precipitated substances and the complex are better polymerized, the chemical balance caused by the reduction of hydroxyl is effectively prevented, and the effects complement each other with the adjustment of pH after the compound medicament is added, so that the efficiency of the compound medicament is maximized;
Coagulant aid: the coagulant aid is used for adjusting or improving coagulation conditions, promoting agents added for coagulation or high molecular substances for improving a flocculating constituent structure, plays a role in bonding and bridging among micro-gel, enables the coagulation to be thick and have a wide surface, fully plays a role in absorbing coiled belts so as to improve clarification effect, and can enable the effect of the composite agent to be better when being matched with organic polymers for use.
The invention has the beneficial effects that:
1. The composite medicament is prepared by compounding the colloidal particle carrier, the ion settling agent and the ammonia removal agent, has a very good effect of removing manganese and ammonia nitrogen, can reduce the concentration of manganese in water to below 1mg/L and the concentration of ammonia nitrogen to below 5mg/L, and has the removal rate of manganese and ammonia nitrogen in wastewater respectively reaching 99.9 percent and more than 99 percent.
2. According to the invention, the addition of the organic polymer can effectively capture manganese ions in the wastewater to form a colloidal substance, and then the colloidal substance is polymerized and adsorbed by a colloidal particle carrier to form a stable precipitate, so that sludge and water are effectively separated; in addition, the organic polymer and the ammonia remover do not have chemical reaction, and the ammonia remover can remove ammonia nitrogen in water in an unimpeded environment, so that the composite agent fully achieves the effect of jointly removing manganese and ammonia nitrogen.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The composite medicament is prepared by compounding a colloidal particle carrier, an ion settling agent and an ammonia remover, wherein the colloidal particle carrier accounts for 30-45% by mass, the ion settling agent accounts for 10-20% by mass, and the ammonia remover accounts for 30-50% by mass.
the colloidal particle carrier is one or two of ferric chloride, ferrous sulfide, ferrous chloride, aluminum sulfate, magnesium sulfate and magnesium chloride.
The ion settling agent is one or two of sodium sulfide, calcium sulfide, aluminum oxide, calcium oxide and magnesium sulfide.
the ammonia remover is one of calcium hypochlorite, sodium hypochlorite and potassium hypochlorite. The coagulant aid is one of polyacrylamide, sodium polyacrylate and polyaluminium chloride.
The composite medicament synthesized according to the proportion is added into wastewater containing 100mg/L-1500mg/L of manganese and 200mg/L-500mg/L of ammonia nitrogen, the mass ratio of the composite medicament to the wastewater is about 1:50-1:150, the pH is controlled between 7.8-9.5, the mixture is stirred at a constant speed for 20-30min, a small amount of organic polymer and coagulant aid (the mass ratio of the organic polymer to the wastewater is about 1:1000-1:2000 and the mass ratio of the organic polymer to the coagulant aid to the wastewater is 1:500-1:1000 respectively) are added, the mixture is stirred slowly for 30min and is kept stand to achieve mud-water separation, and the effluent can reach the primary standard of the comprehensive wastewater discharge standard (GB 8978-.
Example 1
mixing 16% of ferrous sulfide, 16% of ferrous chloride, 10% of calcium sulfide and 8% of aluminum oxide according to mass percentage, stirring at low speed of 30rpm for 10min, adding 50% calcium hypochlorite, stirring at 50rpm, standing for 30min to obtain compound preparation, treating wastewater with the manganese concentration of 600mg/L and the ammonia nitrogen of 300mg/L, adjusting the pH to 8.2, wherein the adding mass ratio (to the wastewater) of the composite medicament is 1:100, stirring at 50rpm for 20min, adding polyacrylamide and dithiocarbamate at a mass ratio of polyacrylamide to wastewater of about 1:1000 and dithiocarbamate to wastewater of about 1:2000, slowly stirring at 20rpm for 30min, standing to separate sludge and water, wherein the manganese concentration of the effluent is 0.45mg/L, the ammonia nitrogen concentration is 2.22mg/L, the manganese removal efficiency is 99.9%, and the ammonia nitrogen removal rate is 99.2%.
example 2
Mixing 16% of ferrous sulfide, 16% of ferric chloride, 12% of calcium oxide and 6% of sodium sulfide according to mass percentage, stirring at a low speed of 30rpm for 20min, then taking 50% of sodium hypochlorite, fully stirring at a 50rpm, standing for 30min to obtain a composite medicament, treating wastewater with the manganese concentration of 200mg/L and the ammonia nitrogen concentration of 200mg/L, adding the composite medicament at a mass ratio (with the wastewater) of 1:150, adjusting the pH to 7.8, stirring at a constant speed of 50rpm for 20min, then adding sodium polyacrylate and trimercapto-triazine trisodium salt, wherein the mass ratio of the sodium polyacrylate to the wastewater is about 1:1000, the mass ratio of the trimercapto-triazine trisodium salt to the wastewater is about 1:2000, slowly stirring at 20rpm for 30min to achieve mud-water separation, the manganese concentration of effluent is 0.18mg/L, the ammonia nitrogen concentration is 1.87mg/L, the manganese removal efficiency is 99.9%, and the ammonia nitrogen removal rate is 99.1%.
Example 3
According to the mass percent, 25% of aluminum sulfate, 20% of magnesium chloride and 10% of calcium oxide are mixed, the mixture is stirred at a low speed of 30rpm for 15min, 45% of calcium hypochlorite is taken, the mixture is fully stirred at a speed of 50rpm and is kept stand for 30min to obtain a composite medicament, wastewater with the manganese concentration of 1000mg/L and the ammonia nitrogen of 400mg/L is treated, the mass ratio of the composite medicament to the wastewater (and the wastewater) is 1:100, the pH value is adjusted to 8.8, the mixture is stirred at a constant speed of 50rpm for 20min, polyaluminium chloride and methyl ethyl sulfur are added, the mass ratio of the polyaluminium chloride to the wastewater is about 1:500, the mass ratio of the methyl ethyl sulfur to the wastewater is about 1:1500, the mixture is slowly stirred at 20rpm for 30min, the mixture is kept stand to achieve mud-water separation, the manganese concentration of effluent is 0.78mg/L, the ammonia nitrogen concentration is 3.87 mg/.
Example 4
According to the mass percent, 20 percent of aluminum chloride, 20 percent of magnesium sulfate and 14 percent of magnesium sulfide are mixed, the mixture is stirred at a low speed of 30rpm for 20min, 46 percent of potassium hypochlorite is taken, the mixture is fully stirred at a speed of 50rpm and is kept stand for 30min to obtain a composite medicament, the wastewater with the manganese concentration of 1500mg/L and the ammonia nitrogen of 500mg/L is treated, the mass ratio of the composite medicament to the wastewater (and the wastewater) is 1:100, the pH value is adjusted to 9.5, the mixture is stirred at a constant speed of 50rpm for 20min, polyacrylamide and trimercapto triazine trisodium salt are added, the mass ratio of the polyacrylamide to the wastewater is about 1:1000, the mass ratio of the trimercapto triazine trisodium salt to the wastewater is about 1:2000, the mixture is slowly stirred at 20rpm for 30min, and the mixture is kept stand to achieve mud-water separation, the manganese concentration of effluent is 1.54mg/L, the ammonia nitrogen concentration is 2.67 mg/.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or other related fields directly or indirectly are included in the scope of the present invention.
Claims (8)
1. The composite medicament for removing manganese and ammonia nitrogen in wastewater is characterized by comprising the following components in percentage by mass: 30-45% of colloidal particle carrier, 10-20% of ion settling agent and 30-50% of ammonia removing agent.
2. the composite reagent for removing manganese and ammonia nitrogen in wastewater according to claim 1, wherein the colloidal particle carrier is one or two of ferric chloride, ferrous sulfide, ferrous chloride, aluminum sulfate, magnesium sulfate and magnesium chloride.
3. The compound reagent for removing manganese and ammonia nitrogen in wastewater according to claim 1, wherein the ion settling agent is one or two of sodium sulfide, calcium sulfide, aluminum oxide, calcium oxide and magnesium sulfide.
4. The composite reagent for removing manganese and ammonia nitrogen in wastewater as claimed in claim 1, wherein the ammonia removing agent is one of calcium hypochlorite, sodium hypochlorite and potassium hypochlorite.
5. The use of the composite agent for removing manganese and ammonia nitrogen in wastewater according to any one of claims 1 to 4, wherein the composite agent is used together with an organic polymer and a coagulant aid.
6. The composite reagent for removing manganese and ammonia nitrogen in wastewater as claimed in claim 5, wherein said organic polymer is one of dithiocarbamate, trimercaptotriazine trisodium salt, and methyl ethyl sulfide.
7. The composite medicament for removing manganese and ammonia nitrogen in wastewater as claimed in claim 5, wherein the coagulant aid is one of polyacrylamide, sodium polyacrylate and polyaluminium chloride.
8. The application method of the composite reagent for removing manganese and ammonia nitrogen in wastewater according to claim 5 is characterized by comprising the following steps:
S1: taking the colloidal particle carrier and the ion settling agent according to a certain proportion, uniformly stirring at a rotating speed of 30rpm, slowly adding the ammonia removing agent, fully stirring at a rotating speed of 50rpm, and standing for 20-40min to obtain a composite medicament;
S2: adding the composite medicament prepared in the step S1 into wastewater with the manganese concentration and the ammonia nitrogen concentration of 100-1500 mg/L and 200-500 mg/L respectively, controlling the mass ratio of the composite medicament to the wastewater to be 1:50-1:150, controlling the pH to be 7.8-9.5, and uniformly stirring at the rotating speed of 50rpm for 20-30min to separate out colloid particles;
S3: adding an organic polymer and a coagulant aid into the wastewater in the step S2, wherein the mass ratio of the organic polymer to the wastewater is 1:100-1:2000, the mass ratio of the coagulant aid to the wastewater is 1:500-1:1000, slowly stirring the mixture for 30min at 20rpm, standing the mixture to separate sludge from water, and the effluent can reach the primary standard of the comprehensive wastewater discharge standard (GB 2-1996).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526724A (en) * | 2021-07-08 | 2021-10-22 | 南方锰业集团有限责任公司大新锰矿分公司 | Low-concentration ammonia nitrogen manganese wastewater treatment system and method using manganese tailings |
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