CN113880319A - Ammonia nitrogen wastewater treatment method and system - Google Patents
Ammonia nitrogen wastewater treatment method and system Download PDFInfo
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Abstract
The invention relates to an ammonia nitrogen wastewater treatment method and system, wherein the solubility product constant of ammonium phosphate manganese is obviously lower than that of manganese salts in other forms, the water quality of the ammonia nitrogen wastewater is firstly adjusted, phosphate solution is added, the pH value is adjusted to be 7-10, then divalent manganese ion solution is added, ammonium ions, phosphate ions and divalent manganese ions are fully reacted to generate ammonium phosphate manganese precipitate, ammonia nitrogen removal is completed through solid-liquid separation, then oxidant is introduced to convert the divalent manganese ions remaining in water into solid manganese dioxide for separation and removal, the ammonia nitrogen removal rate of the obtained water is more than or equal to 90%, the purity of the obtained ammonium phosphate manganese is more than or equal to 85%, and the method has good environmental protection and economic benefits.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method and a system for treating ammonia nitrogen wastewater.
Background
Ammonia nitrogen is a nutrient substance, and is discharged into the natural water environment to cause eutrophication. Therefore, in the modern environmental protection field, great importance is placed on the removal of ammonia nitrogen. In the latest emission standards, strict control indexes are also set for the emission content standards.
For ammonia nitrogen removal, the currently mainly applied technologies are as follows: stripping, chemical precipitation, ion exchange, and biological treatment. The blow-off method is usually used for treating high-concentration ammonia nitrogen index wastewater, the biological method is suitable for treating low-concentration ammonia nitrogen wastewater, and the ion exchange method has certain application limiting conditions because a large amount of regenerated liquid is discharged to cause certain secondary pollution. In contrast, the chemical precipitation method has a wider concentration application range, the final concentration of ammonia nitrogen can be controlled by adding the amount of the medicament, and the engineering use is relatively convenient. However, the chemical precipitation method mainly utilizes the magnesium ammonium phosphate method for treatment at present, and the method has a plurality of problems in application, so that the application is limited. Firstly, the solubility product constant of magnesium ammonium phosphate is too close to that of magnesium phosphate, so that the generation of precipitation side reaction is difficult to control by an effective means in the actual industry, and the removal rate of ammonia nitrogen is limited; secondly, phosphoric acid is a polybasic acid which has various forms in the aqueous solution, which also aggravates the transformation of the form of the substance in the water and then limits the formation of magnesium ammonium phosphate reaction of ammonia nitrogen.
In order to solve the above problems, a precipitation reaction with more remarkable effect is required to remove ammonia nitrogen in wastewater.
Disclosure of Invention
Aiming at the situation, in order to make up for the defects in the prior art, the invention provides an ammonia nitrogen wastewater treatment method and system.
The technical scheme for solving the problems is as follows:
in order to solve the technical problem of ammonia nitrogen wastewater treatment, the invention fully exerts the precipitation characteristic of the ammonium manganese phosphate by analyzing the precipitation characteristic of the ammonium manganese phosphate and combining with the ionic form and combining with engineering reaction control means, so that the ammonia nitrogen can be removed from the water body while the manganese ions are prevented from remaining, and the effective method for removing the ammonia nitrogen from the water is provided.
In order to achieve the above objects and other related objects, a first aspect of the present invention provides a method for treating ammonia nitrogen wastewater, comprising the steps of:
s1, adding a phosphate solution into the ammonia nitrogen wastewater, adjusting the pH to 7-10, adding a divalent manganese ion solution, and performing solid-liquid separation to obtain an ammonium manganese phosphate solid and a clear liquid I;
s2, adding an oxidant into the clear liquid I to convert the divalent manganese ions remained in the clear liquid I into solid manganese dioxide to form manganese dioxide suspension;
and S3, performing membrane separation on the manganese dioxide suspension to obtain clear liquid II, namely the treated water.
Further, the phosphate solution is any one of a phosphoric acid solution, a disodium hydrogen phosphate solution, and a sodium dihydrogen phosphate solution.
Further, the pH adjustment is specifically adding an alkali solution.
Further, the divalent manganese ion solution is a manganese chloride solution or a manganese sulfate solution.
Further, the step S1 includes stirring after the divalent manganese ion solution is added.
Further, the solid-liquid separation is selected from gravity settling, filter cloth filtration or membrane filtration.
Further, the molar ratio of the divalent manganese ions to the ammonium ions is 1.2-1.5: 1.
Further, the molar ratio of the ammonium ions to the phosphate ions is 1: 1-1.1.
Further, the oxidant is one or a combination of a plurality of air, oxygen, sodium hypochlorite, hydrogen peroxide or peroxide.
Further, the step S2 includes stirring after the oxidant is added.
Further, the accuracy of the membrane separation in step S3 is less than 5 μm.
According to the ammonia nitrogen wastewater treatment method provided by the invention, the ammonia nitrogen removal rate of produced water is more than or equal to 90%, and the purity of the obtained ammonium manganese phosphate is more than 85%.
The invention provides a second aspect of an ammonia nitrogen wastewater treatment system, which comprises a reaction tank I, a reaction tank II, a solid-liquid separation device, an oxidation reaction tank and a membrane separation device which are sequentially in fluid communication;
the reaction tank I is provided with an ammonia nitrogen wastewater inlet, a phosphate solution inlet, an alkaline solution inlet and an adjusted wastewater outlet and is used for adjusting the quality of the ammonia nitrogen wastewater;
the reaction tank II is provided with an adjusted wastewater inlet, a divalent manganese ion solution inlet and a reacted water outlet and is used for enabling the ammonium manganese phosphate solution to fully react; the adjusted wastewater inlet is communicated with the adjusted wastewater outlet of the reaction tank I;
the solid-liquid separation device is provided with a water inlet after reaction and a clear liquid I outlet and is used for separating ammonium manganese phosphate precipitated in the water body through reaction; the reacted water inlet is communicated with the reacted water outlet of the reaction tank II;
the oxidation reaction tank is provided with a clear liquid I inlet, an oxidant adding inlet and a manganese dioxide suspension outlet and is used for converting bivalent manganese ions in a water body into solid manganese dioxide; the inlet of the clear liquid I is communicated with the outlet of the clear liquid I of the solid-liquid separation device;
the membrane separation device is provided with a manganese dioxide suspension inlet and a clear liquid II outlet and is used for separating manganese dioxide precipitated in a water body through reaction; and the manganese dioxide suspension inlet is communicated with the manganese dioxide suspension outlet of the oxidation reaction tank.
The method is mainly used for treating ammonia nitrogen wastewater, the solubility product constant of the ammonium phosphate manganese is obviously lower than that of manganese salts in other forms, the ammonia nitrogen wastewater is firstly subjected to water quality adjustment, phosphate solution is added, the pH value is adjusted to be 7-10, then divalent manganese ion solution is added, ammonium ions, phosphate ions and divalent manganese ions are fully reacted to generate ammonium phosphate manganese precipitate, ammonia nitrogen removal is completed through solid-liquid separation, then oxidant is introduced to convert the divalent manganese ions remaining in a water body into solid manganese dioxide for separation and removal, the ammonia nitrogen removal rate of the obtained produced water is more than or equal to 90%, the purity of the obtained ammonium phosphate manganese is more than 85%, and the method has good environmental protection and economic benefits.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the ammonia nitrogen wastewater treatment method provided by the invention, the phosphate solution is added firstly, the pH value is adjusted, then the divalent manganese ion solution is added, and the ammonium manganese phosphate is generated through reaction by controlling the proportion of ammonium and manganese.
2. The ammonium manganese phosphate has definite substance molecular configuration and single product category, can complete ammonia nitrogen removal through reaction, and simultaneously converts the ammonium manganese phosphate into the product of the ammonium manganese phosphate for ion recovery, thereby creating beneficial economic value; the manganese ions remained in the water body are converted into solid manganese dioxide which can be completely separated from the water body through precise filtration through oxidation, and the conversion process is convenient and controllable, so that the residual quantity of the manganese ions is extremely small, and the water production guarantee is good.
3. The ammonia nitrogen wastewater treatment system provided by the invention is simple to control, low in operation cost and strong in impact resistance, can treat ammonia nitrogen wastewater with different concentrations by adjusting the dosage, is stable in water production quality and is convenient to popularize.
Drawings
FIG. 1 is a schematic view of an ammonia nitrogen wastewater treatment system according to a preferred embodiment of the present invention.
FIG. 2 is a schematic view of an ammonia nitrogen wastewater treatment system according to another preferred embodiment of the present invention.
Wherein, 1-a reaction tank I; 2-reaction tank II; 3-a solid-liquid separation device; 4-an oxidation reaction tank; 5-a membrane separation device; 51-a membrane separation tank; 52-an immersed ceramic membrane; 53-suction water pump; 54-a tubular separation membrane; 55-a booster water pump; a 001-phosphate solution inlet; 002-alkali liquor inlet; a liquid inlet for a 003-divalent manganese ion solution; 004-an oxidant addition port.
Detailed Description
An ammonia nitrogen wastewater treatment method comprises the following steps:
s1, adding a phosphate solution into the ammonia nitrogen wastewater, adjusting the pH to 7-10, adding a divalent manganese ion solution, and performing solid-liquid separation to obtain solid ammonium manganese phosphate and clear liquid I (excessive divalent manganese ions remain in the clear liquid I);
s2, adding an oxidant into the clear liquid I to convert the divalent manganese ions remained in the clear liquid I into solid manganese dioxide to form manganese dioxide suspension;
and S3, performing membrane separation on the manganese dioxide suspension (completely removing solid substances in the manganese dioxide suspension) to obtain clear liquid II, namely the treated water (qualified ammonia nitrogen treatment and no divalent manganese residue).
The method can treat ammonia nitrogen wastewater with different concentrations, ensures the final concentration control of ammonia nitrogen by adjusting the addition of phosphate solution, divalent manganese ion solution and oxidant, and has high process flexibility. In some preferred embodiments of the invention, the ammonia nitrogen wastewater is effluent after pretreatment and impurity removal.
In the present invention, the phosphate solution is a phosphate group-containing aqueous solution having high solubility. In some preferred embodiments of the present invention, the phosphate solution is any one of a phosphoric acid solution, a disodium hydrogen phosphate solution, and a sodium dihydrogen phosphate solution.
In some embodiments of the invention, the adjusting the pH is specifically adding a base solution. The alkali solution in the invention is alkali aqueous solution. In some preferred embodiments of the invention, the alkali solution is a sodium hydroxide solution.
The divalent manganese ion solution is an aqueous solution containing divalent manganese ions. In a preferred embodiment of the present invention, the divalent manganese ion solution is a manganese chloride solution or a manganese sulfate solution.
In a preferred embodiment of the present invention, after the divalent manganese ion solution is added in step S1, stirring is further performed, so that ammonium ions, phosphate ions and divalent manganese ions fully react to generate ammonium-manganese phosphate precipitate. More preferably, the stirring Reynolds number is 50000-1000000, and the time is 1-5 hours.
In a preferred embodiment of the present invention, the solid-liquid separation in step S1 is selected from gravity settling, filter cloth filtration or membrane filtration; preferably a gravity settling tank, a filter cloth type filtration device or a membrane filtration device is used. More preferably, the concentration of suspended matters in the water after the solid-liquid separation is less than 30 ppm.
In a preferred embodiment of the invention, the molar ratio of the divalent manganese ions to the ammonium ions is 1.2-1.5: 1. Under the control condition of the optimized molar ratio, the removal rate of the ammonium ions can reach more than 90 percent. If the molar ratio is too low, the ammonia nitrogen removal effect is obviously poor. If the molar ratio is too high, the divalent manganese ion residue is obviously too high, so that the consumption ratio of the subsequent medicine-adding medicament is too high.
In a preferred embodiment of the invention, the molar ratio of the ammonium ions to the phosphate ions is 1: 1-1.1. The ammonium ions and the phosphate radical can effectively react under the condition of the preferred molar ratio, and theoretically, the molar ratio of 1:1, the final reaction target can be completed, so that a small amount of excessive phosphate radical is kept, the formation of ammonium phosphate and manganese is more favorably controlled, excessive reaction is caused if excessive phosphate radical is added, the consumption of a medicament is too high, and the phosphorus element in the treated tail water is easy to exceed the standard.
In a preferred embodiment of the present invention, the oxidant is one or a combination of several of air, oxygen, sodium hypochlorite, hydrogen peroxide and peroxide. In some embodiments of the invention, the oxidant is air, and preferably, the gas-water ratio is controlled to be 6-15: 1. The value is determined by combining the ammonium group concentration, the manganese ion excess degree, the oxygen transfer efficiency and the air utilization efficiency in order to control the reaction stirring intensity and the theoretical oxygen demand generated by manganese dioxide in the actual reaction process. For example, in the case of ammonium ion of 50mg/L, manganese ion required for the reaction is 2.8mmol/L, and considering that the excess amount is 50%, the residual manganese ion is 1.4mmol/L, and the amount of oxygen reacted therewith is 1.4 mmol/L. The molecular weight of the oxygen is 32g/mol, and the required oxygen amount is 44 mg/L. If the oxygen transfer efficiency is 8 percent, the air utilization efficiency is 85 percent, and the oxygen mass ratio is 21 percent, the theoretically required air quantity is calculated to be 3.1L/L. Generally, the excess rate is about 100-500%, so that the gas-water ratio is actually controlled to be 6-15. In a more preferred embodiment of the invention, the oxidant is air, and the gas-water ratio is controlled to be 10: 1. In other embodiments of the present invention, after the step S2 of adding the oxidant, stirring is further included, and the added oxidant is uniformly mixed with the clear solution i by stirring, so that the divalent manganese ions remaining in the water body can be sufficiently oxidized to generate solid manganese dioxide, and the manganese ions in the water body can be completely removed as much as possible.
In a preferred embodiment of the present invention, in the step S3, the membrane separation is performed by using a microfiltration membrane, and the filtration precision of the microfiltration membrane is 0.1 to 5 μm, so that the generated manganese dioxide is completely separated from the water body.
An ammonia nitrogen wastewater treatment system is shown in figure 1 and comprises a reaction tank I1, a reaction tank II 2, a solid-liquid separation device 3, an oxidation reaction tank 4 and a membrane separation device 5 which are sequentially in fluid communication;
the reaction tank I1 is provided with an ammonia nitrogen wastewater inlet, a phosphate solution inlet 001, an alkali solution inlet 002 and an adjusted wastewater outlet and is used for adjusting the quality of ammonia nitrogen wastewater;
the reaction tank II 2 is provided with an adjusted wastewater inlet, a divalent manganese ion solution inlet 003 and a reacted water outlet and is used for fully reacting the ammonium manganese phosphate solution; the adjusted wastewater inlet is communicated with the adjusted wastewater outlet of the reaction tank I1;
the solid-liquid separation device 3 is provided with a water inlet after reaction and a clear liquid I outlet and is used for separating ammonium manganese phosphate precipitated in the water body through reaction; the reacted water inlet is communicated with the reacted water outlet of the reaction tank II 2;
the oxidation reaction tank 4 is provided with a clear liquid I inlet, an oxidant adding inlet 004 and a manganese dioxide suspension outlet and is used for converting bivalent manganese ions in a water body into solid manganese; the inlet of the clear liquid I is communicated with the outlet of the clear liquid I of the solid-liquid separation device 3;
the membrane separation device 5 is provided with a manganese dioxide suspension inlet and a clear liquid II outlet and is used for separating manganese dioxide precipitated in a water body through reaction; the manganese dioxide suspension inlet is communicated with the manganese dioxide suspension outlet of the oxidation reaction tank 4.
In some embodiments of the present invention, the reaction tank i 1 further includes a water inlet pipeline communicated with the ammonia nitrogen wastewater inlet, the phosphate solution inlet 001 and the alkaline solution inlet 002 are disposed on the water inlet pipeline to ensure that the inlet water of the reaction tank i contains a sufficient amount of phosphate ions, and then the alkaline solution is added to adjust the pH of the water body after the phosphate solution is added to a desired range. In other embodiments of the invention, the reaction tank I1 is provided with a stirring device for stirring ammonia nitrogen wastewater; the phosphate solution inlet 001 and the alkali solution inlet 002 are arranged on the reaction tank I1, the phosphate solution and the alkali solution are directly added into the reaction tank I1, and are uniformly mixed with the water body under the stirring action of the stirring device, so that the adjusted wastewater contains enough phosphate ions and reaches the required pH range.
In some embodiments of the invention, the reaction tank ii 2 is further provided with a stirring device for uniformly mixing the divalent manganese ion solution and the adjusted wastewater, and the phosphate radical, the ammonium radical and the divalent manganese ion are sufficiently reacted by the stirring action of the stirring device to generate an ammonium-manganese phosphate solid, thereby completing ammonia nitrogen removal.
In some embodiments of the present invention, the reaction tank ii 2 further includes a communication pipe for communicating the adjusted wastewater inlet with the adjusted wastewater outlet of the reaction tank i 1, and the divalent manganese ion solution inlet 003 is disposed on the communication pipe and is configured to add a divalent manganese ion solution to the adjusted wastewater. In other embodiments of the present invention, the divalent manganese ion solution inlet 003 is disposed on the reaction tank II 2.
In some preferred embodiments of the present invention, the solid-liquid separation device 3 is selected from a gravity type sedimentation tank, a filter cloth type filtration device or a membrane filtration device, so that the generated manganese ammonium phosphate is completely separated from the water body.
In some preferred embodiments of the present invention, the membrane separation device 5 is selected from a submerged ceramic membrane filtration apparatus or a tubular separation membrane apparatus, such that the resulting manganese dioxide is completely separated from the body of water. In some preferred embodiments of the present invention, the membrane separation device 5 is an immersed ceramic membrane filtration apparatus, and includes a membrane separation tank 51, an immersed ceramic membrane 52 disposed in the membrane separation tank, and a suction water pump 53 connected to a membrane module of the immersed ceramic membrane 52. In other more preferred embodiments of the present invention, the membrane separation device 5 is a tubular separation membrane apparatus, comprising a tubular separation membrane 54 and a booster water pump 55 connected to the tubular separation membrane 54 for boosting the pressure of the water supplied to the tubular separation membrane.
In some embodiments of the present invention, when the oxidant is a gas (air or oxygen), the oxidation reaction tank 4 is further connected to a blower, and an air outlet of the blower is communicated with the oxidant inlet 004 of the oxidation reaction tank 4, so that the gas oxidant can fully contact with the water body, and oxidation of divalent manganese in the water body is promoted. In some preferred embodiments of the present invention, the oxidant inlet 004 is located at the bottom of the oxidation reaction tank 4, and an aeration device communicated with the oxidant inlet 004 is further disposed in the oxidation reaction tank 4, so as to facilitate mixing of the gaseous oxidant and the water body, and to perform a stirring function, so that the oxidation reaction is more complete.
In other embodiments of the present invention, when the oxidizing agent is liquid (hydrogen peroxide) or solid (sodium hypochlorite or peroxide), the oxidation reaction tank 4 is provided with a stirring device for uniformly mixing the clear liquid i and the oxidizing agent, so that the oxidizing agent can fully contact with the divalent manganese ions remaining in the clear liquid i, the divalent manganese ions can be completely oxidized to generate solid manganese dioxide, and complete removal of the manganese ions in the water body is ensured.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The following examples all treat ammonia nitrogen wastewater produced by a certain domestic chemical plant: the ammonia nitrogen concentration is 200 mg/L. The ammonia nitrogen removal was calculated using the following formula:
NH3-N removal rate (C in-C out)/C in 100% (1)
In the formula: c, monitoring the concentration of the ammonia nitrogen at the inlet; and C, outlet is outlet ammonia nitrogen monitoring concentration.
Example 1
The ammonia nitrogen wastewater treatment system of the embodiment is shown in figure 1, and the ammonia nitrogen wastewater treatment amount is 5m3The ammonia nitrogen removal capacity is about 0.45 kg/day per day, and the yield of the ammonium phosphate manganese is 5.5 kg/day.
S1, conveying the collected ammonia nitrogen wastewater into a reaction tank I1 by a water conveying pump, arranging a phosphate solution inlet 001 and an alkali solution inlet 002 on a water inlet pipeline communicated with an ammonia nitrogen wastewater inlet of the reaction tank I1, adding 5 wt% of sodium dihydrogen phosphate solution from the phosphate solution inlet 001 to ensure that the inlet water contains enough phosphate ions, adding 5 wt% of sodium hydroxide solution from the alkali solution inlet 002 to adjust the pH of the inlet water, and controlling the molar ratio of ammonium ions to the phosphate ions to be 1:1.1 and the pH to be 8.5. And (2) the adjusted wastewater enters a reaction tank II 2, 1 wt% of manganese chloride solution is added into a divalent manganese ion solution inlet 003 arranged on a communicating pipeline for communicating the adjusted wastewater inlet with the adjusted wastewater outlet of the reaction tank I1, the molar ratio of divalent manganese ions to ammonium ions is controlled to be 1.4:1, a stirring device of the reaction tank II is started, after the reaction in the reaction tank II 2 is carried out for 3 hours, a water body after the reaction flows through a gravity type sedimentation tank 3 for solid-liquid separation, the obtained ammonium manganese phosphate solid is discharged from the lower part of the gravity type sedimentation tank 3, the obtained clear liquid I is discharged from the upper part, and the concentration of suspended matters in the clear liquid I is ensured to be lower than 30ppm after the solid-liquid separation.
S2, feeding the clear liquid I discharged from the gravity type sedimentation tank 3 into an oxidation reaction tank 4, starting a blower connected with the oxidation reaction tank 4, introducing air into a water body through an oxidant inlet 004 at the bottom of the oxidation reaction tank 4, fully contacting the air with the clear liquid I through an aeration device, oxidizing, controlling the ratio of air to water to be 10:1, and fully reacting to obtain manganese dioxide suspension.
And S3, treating the manganese dioxide suspension in an immersed ceramic membrane filtration device 5, wherein the manganese dioxide suspension firstly enters a membrane separation tank 51, then is subjected to membrane separation by an immersed ceramic membrane 52 in the membrane separation tank 51, the manganese dioxide solid obtained by separation is discharged from the bottom of the membrane separation device 5, and the separated clear liquid II is discharged by a suction water pump 53, namely the produced water.
After the treatment of the system, the ammonia nitrogen concentration in the obtained produced water is 20mg/L, the ammonia nitrogen removal rate is 90%, the purity of the ammonium manganese phosphate in the obtained ammonium manganese phosphate solid is more than 85% (wt), and the residual manganese ion concentration is 0.07 mg/L.
Example 2
The ammonia nitrogen wastewater treatment system of the embodiment is shown in figure 2, and the ammonia nitrogen wastewater treatment amount is 20m3The ammonia nitrogen removal capacity is about 0.9 kg/day per day, and the yield of the ammonium phosphate manganese is 67 kg/day.
S1, conveying the collected ammonia nitrogen wastewater to a reaction tank I1 by a water conveying pump, wherein the reaction tank I is provided with a stirring device for stirring the ammonia nitrogen wastewater; and a phosphate solution inlet 001 and an alkaline solution inlet 002 are further arranged on the reaction tank I, a stirring device is started, 5 wt% of sodium dihydrogen phosphate solution is added from the phosphate solution inlet 001 to ensure that the wastewater contains enough phosphate ions, 3 wt% of sodium hydroxide solution is added from the alkaline solution inlet 002 to adjust the pH value of the wastewater, and the molar ratio of the ammonium ions to the phosphate ions is controlled to be 1:1, and the pH value is controlled to be 9. And (2) the adjusted wastewater enters a reaction tank II 2, 1 wt% of manganese chloride solution is added through a divalent manganese ion solution inlet 003 on the reaction tank II 2, the molar ratio of divalent manganese ions to ammonium ions is controlled to be 1.5:1, a stirring device of the reaction tank II is started, after the reaction in the reaction tank II 2 is carried out for 2 hours, a water body after the reaction flows through a gravity type sedimentation tank I3 for solid-liquid separation, the obtained ammonium manganese phosphate solid is discharged from the lower part of the gravity type sedimentation tank 3, the obtained clear liquid I is discharged from the upper part, and the concentration of suspended matters in the clear liquid I is ensured to be lower than 30ppm after the solid-liquid separation.
S2, enabling clear liquid I obtained after the clear liquid I passes through the gravity type sedimentation tank 3 to enter an oxidation reaction tank 4, starting a stirring device of the oxidation reaction tank 4, adding 3 wt% of hydrogen peroxide solution into a water body through an oxidant adding port 004 to carry out oxidation reaction, uniformly mixing the hydrogen peroxide solution with the clear liquid I under the stirring action, and oxidizing bivalent manganese remained in the clear liquid I into manganese dioxide solid particles to be separated out from the water body to obtain manganese dioxide suspension.
And S3, allowing the manganese dioxide suspension to enter a tubular separation membrane device 5 for treatment, increasing the water supply pressure through a tubular separation membrane water pump 55, then allowing the manganese dioxide suspension to enter a tubular separation membrane 54 for separation to obtain solid manganese dioxide and clear liquid II, discharging the solid manganese dioxide obtained by separation from the top of the membrane separation device 5, and discharging the clear liquid II obtained by separation from the middle to obtain the produced water.
After the treatment by the system, the ammonia nitrogen concentration in the obtained produced water is 10mg/L, the purity of the ammonium manganese phosphate in the obtained ammonium manganese phosphate solid is more than 85% (wt), and the residual manganese ions are not detected.
The invention provides an optimized ammonia nitrogen wastewater treatment method, which comprises the steps of taking manganese chloride or manganese sulfate as a manganese source reactant, taking phosphate as a phosphorus source reactant, carrying out reaction in a communicated reactor, generating ammonium phosphate manganese precipitate by controlling the proportion of ammonium and manganese to complete the complete removal of ammonia nitrogen (the ammonia nitrogen removal efficiency can be greatly improved due to the moderate excess of manganese ions), and simultaneously converting residual manganese source reactant into manganese dioxide solid precipitate by an oxidation mode (the moderate excess of an oxidant), thereby completing the removal of final pollutants and ensuring that the residual quantity of manganese ions in produced water is very small. The method for treating the ammonia nitrogen wastewater provided by the invention has the characteristics of easier reaction control, high ammonia nitrogen removal efficiency, less pollutant residue in water, capability of completing the recovery of ammonia nitrogen nutrient substances and the like.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The ammonia nitrogen wastewater treatment method is characterized by comprising the following steps:
s1, adding a phosphate solution into the ammonia nitrogen wastewater, adjusting the pH to 7-10, adding a divalent manganese ion solution, and performing solid-liquid separation to obtain an ammonium manganese phosphate solid and a clear liquid I;
s2, adding an oxidant into the clear liquid I to convert the divalent manganese ions remained in the clear liquid I into solid manganese dioxide to form manganese dioxide suspension;
and S3, performing membrane separation on the manganese dioxide suspension to obtain clear liquid II, namely the treated water.
2. The ammonia nitrogen wastewater treatment method of claim 1, characterized by further comprising at least one of the following technical characteristics:
1) the phosphate solution is any one of a phosphoric acid solution, a disodium hydrogen phosphate solution and a sodium dihydrogen phosphate solution;
2) the pH is specifically adjusted by adding an alkali solution;
3) the divalent manganese ion solution is a manganese chloride solution or a manganese sulfate solution;
4) step S1, adding the divalent manganese ion solution and then stirring;
5) the solid-liquid separation is selected from gravity settling, filter cloth filtration or membrane filtration;
6) the molar ratio of the ammonium ions to the phosphate ions is 1: 1-1.1;
7) the molar ratio of the divalent manganese ions to the ammonium ions is 1.2-1.5: 1;
8) the oxidant is one or a compound of a plurality of air, oxygen, sodium hypochlorite, hydrogen peroxide or peroxide;
9) step S2, adding an oxidant and then stirring;
10) the precision of the membrane separation in step S3 is less than 5 μm;
11) the ammonia nitrogen removal rate of the produced water is more than or equal to 90 percent, and the purity of the obtained ammonium manganese phosphate is more than 85 percent.
3. The ammonia nitrogen wastewater treatment method of claim 2, characterized by further comprising at least one of the following technical characteristics:
i. in the feature 2), the alkali solution is a sodium hydroxide solution;
in the feature 4), the stirring control stirring reynolds number is 50000-1000000, and the time is 1-5 hours;
in the characteristic 5), the concentration of suspended matters in water after solid-liquid separation is less than 30 ppm;
iv, in the characteristic 8), when the oxidant is air, controlling the gas-water ratio to be 6-15: 1.
4. An ammonia nitrogen wastewater treatment system is characterized by comprising a reaction tank I (1), a reaction tank II (2), a solid-liquid separation device (3), an oxidation reaction tank (4) and a membrane separation device (5) which are sequentially in fluid communication;
the reaction tank I (1) is provided with an ammonia nitrogen wastewater inlet, a phosphate solution inlet (001), an alkali solution inlet (002) and an adjusted wastewater outlet and is used for adjusting the quality of the ammonia nitrogen wastewater;
the reaction tank II (2) is provided with an adjusted wastewater inlet, a divalent manganese ion solution inlet (003) and a reacted water outlet and is used for fully reacting the ammonium manganese phosphate solution; the adjusted wastewater inlet is communicated with the adjusted wastewater outlet of the reaction tank I (1);
the solid-liquid separation device (3) is provided with a water inlet after reaction and a clear liquid I outlet and is used for separating ammonium phosphate and manganese separated out by the reaction in the water; the reacted water inlet is communicated with the reacted water outlet of the reaction tank II (2);
the oxidation reaction tank (4) is provided with a clear liquid I inlet, an oxidant adding inlet (004) and a manganese dioxide suspension liquid outlet and is used for converting bivalent manganese ions in a water body into solid manganese dioxide; the inlet of the clear liquid I is communicated with the outlet of the clear liquid I of the solid-liquid separation device (3);
the membrane separation device (5) is provided with a manganese dioxide suspension inlet and a clear liquid II outlet and is used for separating solid manganese dioxide precipitated by reaction in a water body; the manganese dioxide suspension inlet is communicated with the manganese dioxide suspension outlet of the oxidation reaction tank (4).
5. The ammonia nitrogen wastewater treatment system of claim 4, further comprising any one of the following technical features:
(1) the reaction tank I (1) also comprises a water inlet pipeline communicated with the ammonia nitrogen wastewater inlet, and the phosphate solution inlet (001) and the alkaline solution inlet (002) are arranged on the water inlet pipeline;
(2) the reaction tank I (1) is provided with a stirring device for stirring ammonia nitrogen wastewater; the phosphate solution inlet (001) and the alkali solution inlet (002) are arranged on the reaction tank I (1).
6. The ammonia nitrogen wastewater treatment system of claim 4, wherein the reaction tank II (2) is further provided with a stirring device for uniformly mixing the divalent manganese ion solution and the adjusted wastewater.
7. The ammonia nitrogen wastewater treatment system of claim 4, wherein the reaction tank II (2) further comprises a communicating pipeline for communicating the adjusted wastewater inlet with the adjusted wastewater outlet of the reaction tank I (1), and the divalent manganese ion solution inlet (003) is arranged on the communicating pipeline and is used for adding a divalent manganese ion solution into the adjusted wastewater.
8. The ammonia nitrogen wastewater treatment system of claim 4, further comprising at least one of the following technical features:
a) the solid-liquid separation device (3) is selected from a gravity type sedimentation tank, filter cloth type filtering equipment or membrane filtering equipment;
b) and the membrane separation device (5) is selected from immersed ceramic membrane filtration equipment or tubular separation membrane equipment.
9. The ammonia nitrogen wastewater treatment system of claim 4, further comprising at least one of the following technical features:
(a) the oxidation reaction tank (4) is connected with a blower, and an air outlet of the blower is communicated with an oxidant feeding port (004) of the oxidation reaction tank (4);
(b) and the oxidation reaction tank (4) is provided with a stirring device for uniformly mixing the clear liquid I and the oxidant.
10. The ammonia-nitrogen wastewater treatment system according to claim 9, wherein in the characteristic (a), the oxidant inlet (004) is located at the bottom of the oxidation reaction tank (4), and an aeration device communicated with the oxidant inlet (004) is further arranged in the oxidation reaction tank (4).
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