CN113087319A - System and method for treating rare earth or nonferrous smelting high-salt high-COD wastewater - Google Patents
System and method for treating rare earth or nonferrous smelting high-salt high-COD wastewater Download PDFInfo
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Abstract
A system and method for treating rare earth or nonferrous smelting high-salt high-COD wastewater belongs to the technical field of industrial high-salt wastewater treatment, and comprises a pretreatment oil removal unit, a desalination deamination unit, a sludge microorganism domestication unit, a biochemical treatment unit and a high-grade oxidation treatment unit; the outlet of the pretreatment oil removal unit is connected with the inlet of the desalination and deamination unit; the outlet of the desalting and deamination unit and the outlet of the sludge microorganism domestication unit are connected with the inlet of the biochemical treatment unit; the outlet of the biochemical treatment unit is connected with the inlet of the advanced oxidation treatment unit. According to the invention, through pretreatment oil removal, calcium salt desalination and deamination, sludge microorganism domestication, biochemical treatment and advanced oxidation treatment, on one hand, the salinity of the wastewater is reduced, and ammonium is recycled, and on the other hand, the sludge microorganisms are domesticated to improve the salt tolerance of the wastewater, so that the high-salinity high-COD wastewater can be treated by a biochemical method; and advanced oxidation method is adopted for advanced treatment on the basis of biochemical treatment, so that the high-salt high-COD wastewater can be reused or discharged after reaching the standard.
Description
Technical Field
The invention belongs to the technical field of industrial high-salinity wastewater treatment, and relates to a system and a method for treating rare earth or nonferrous smelting high-salinity high-COD wastewater.
Background
The rare earth or nonferrous smelting industry belongs to the high pollution industry, and is generally embodied in high-salt organic pollutant wastewater which has high salt content (mainly ammonium sulfate, generally more than 100 g/L) and contains a large amount of organic matters (high COD value). The waste water has great harm to human body, crop growth, ecological environment and the like, so the waste water can not be discharged and recycled, and great trouble is brought to enterprises. Therefore, new methods are needed to solve the problem of wastewater disposal. The method for treating the smelting high-salt high-COD wastewater at present mainly comprises the following steps:
(1) the membrane separation method is a novel water treatment technology. It mainly uses a special semipermeable membrane to separate solute from solvent in the solution, so as to attain the goal of separating and purifying water quality. However, the processing effect is greatly related to the quality of the membrane, and if a good effect is required, a more expensive membrane is required, and a large pressure is required to realize the effect, which inevitably causes a multiple increase in cost. However, as COD of the high-salt organic matter smelting wastewater is high, part of macromolecules can pollute the membrane, and the permeability and the service life of the membrane are obviously reduced.
(2) The electrolysis method can effectively reduce COD in the wastewater, but has the defects of higher operation cost and being uneconomical for degrading the high-COD wastewater.
(3) The method is a novel wastewater zero-discharge technology, and is characterized in that wastewater is concentrated through a series of methods, concentrated solution is evaporated and crystallized, steam is condensed and recovered, and salt crystals are dried into industrial salt, so that the aim of wastewater zero discharge is fulfilled. However, the smelting high-salt wastewater contains more organic matters, the quality of salt is greatly influenced, and the method has extremely high energy consumption and high cost.
The traditional method for reducing the COD of the wastewater comprises a biochemical method, an advanced oxidation method and the like. However, the biochemical method has certain applicable conditions for removing COD, the tolerance degree of biological bacteria to salt is low, the wastewater with the salt content of more than 10g/L is difficult to carry out COD degradation by the biochemical method, and the rare earth or nonferrous smelting high-salt high-COD wastewater cannot be treated by the traditional biochemical method. The traditional advanced oxidation technology has the defects of large medicament consumption, high energy consumption and the like, and the cost is hard to bear if the rare earth or nonferrous smelting high-salt high-COD wastewater is treated by adopting the advanced oxidation method.
People urgently need a method with good treatment effect and low operation cost for treating rare earth or nonferrous smelting high-salt and high-COD wastewater.
Disclosure of Invention
The invention aims to provide a system and a method for treating rare earth or nonferrous smelting high-salt and high-COD wastewater, which mainly aim at the high-salt and high-COD wastewater of an ammonium sulfate system in the rare earth or nonferrous smelting industry, and reduce the salinity of the wastewater to recycle ammonium and domesticate sludge microorganisms to improve the salt tolerance of the sludge microorganisms by 'pretreatment oil removal-calcium salt desalinization and deamination-sludge microorganism domestication-biochemical treatment-advanced oxidation treatment', so that the high-salt and high-COD wastewater can be treated by a biochemical method; and advanced oxidation treatment is adopted on the basis of biochemical treatment, so that the high-salt high-COD wastewater can be recycled or discharged after reaching the standard. The system and the method provided by the invention solve the problem that a series of COD (chemical oxygen demand) removal methods such as biochemical method can not be used for removing COD due to overhigh salt content and biological bacteria survival inhibition, and advanced oxidation method has overhigh treatment cost on a high-salt and high-COD system, and can recover water resources to the maximum extent and reduce running wastewater.
In order to achieve the above object, the present invention adopts the following technical solutions.
A system for treating high-salinity high-COD wastewater generated in rare earth or nonferrous smelting is characterized by comprising a pretreatment oil removal unit, a desalination and deamination unit, a sludge microorganism domestication unit, a biochemical treatment unit and a high-grade oxidation treatment unit; the outlet of the pretreatment oil removal unit is connected with the inlet of the desalination and deamination unit; the outlet of the desalting and deamination unit and the outlet of the sludge microorganism domestication unit are connected with the inlet of the biochemical treatment unit; the outlet of the biochemical treatment unit is connected with the inlet of the advanced oxidation treatment unit.
Further, the rare earth or nonferrous smelting high-salt and high-COD wastewater is characterized in that: pH value is 5-10, COD is 2000-4 2-Is 50-200g/L, NH4 +Is 400g/L for 100-.
Further, the pretreatment oil removal unit comprises a coalescence oil removal device, an active carbon oil removal device and a filtration oil removal device.
Further, the desalination and deamination unit comprises a calcium salt feeding device and an ammonia gas absorption device. Preferably, the calcium salt is a calcium salt compounded by calcium hydroxide, calcium carbonate, calcium chloride, calcium oxide and sodium hydroxide.
Further, the sludge microorganism domestication unit comprises a plurality of microorganism culture devices, and culture solution and wastewater with different proportions are added into the microorganism culture devices. The salinity in the microorganism culture device is gradually improved by gradually improving the proportion of the wastewater, and the salt tolerance of the sludge microorganisms is improved by acclimatization. Preferably, the culture solution comprises the following components: 1-2g/L glucose, 0.01-0.1g/L sodium phosphate, 0.01-0.1g/L potassium dihydrogen phosphate, 0.01-0.1g/L calcium chloride, 0.01-0.1g/L magnesium sulfate and 0.01-0.02g/L ferrous sulfate. Preferably, the strain of the sludge microorganism comes from the bottom sediment of the sewage outlet of the smelting wastewater and is obtained by separation and purification means.
Further, the biochemical treatment unit comprises a domesticated sludge microorganism adding device and an aeration device. Preferably, the aeration device is an aeration disc, and the aeration quantity ensures that the oxygen content of the water body is 1-4 mg/L.
Further, the advanced oxidation unit comprises an ozone source, an ozone aeration device and an ozone tail gas destruction device. Preferably, the ozone tail gas destruction device is connected with an aeration device of the biochemical treatment unit, and oxygen generated after the ozone tail gas is destroyed enters the biochemical treatment unit for aeration.
The method for treating the rare earth or nonferrous smelting high-salt high-COD wastewater by adopting the system provided by the invention comprises the following steps:
(1) the wastewater enters a pretreatment oil removal unit for treatment, and the dangerous waste generated by pretreatment oil removal is subjected to centralized treatment;
(2) the pretreated and deoiled wastewater enters a desalting and deaminating unit, calcium salt is added according to the molar ratio of calcium to sulfate radical of 1-5: 1, the mixture is stirred and reacted for 10-30 min, precipitation and filtration are carried out, and the pH value of filtrate is adjusted to 6-8; recovering the volatilized ammonia gas through an ammonia gas absorption device;
(3) acclimating the sludge microorganisms by a sludge microorganism acclimation unit with an acclimation period of 20-40 days;
(4) the filtrate obtained after the pH value is adjusted in the step (2) and the sludge microorganisms domesticated in the step (3) enter a biochemical treatment unit for treatment;
(5) and (4) discharging water from the biochemical treatment unit, and entering an ozone catalytic oxidation unit for advanced treatment.
Further, the salt content of the filtrate in the step (2) is 10-20 g/L.
Further, the COD value of the biochemical treatment unit in the step (4) is reduced by more than 80%, and the COD value of the final effluent in the step (5) is below 60 mg/L.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a system and a method for treating rare earth or nonferrous smelting high-salt and high-COD wastewater, which can effectively degrade organic pollutants in the high-salt wastewater, recover ammonia water, and finally discharge water with COD below 60mg/L for recycling or standard discharge. Compared with other processes, the invention overcomes the problems that organic matters in the high-salinity wastewater are difficult to degrade, especially cannot be explained by a biochemical method, and the treatment cost is high. The method can be used for treating rare earth or nonferrous smelting high-salinity wastewater.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The technical scheme of the invention is clearly and completely described below by combining the attached drawings of the specification. It is to be understood that the described embodiments are merely exemplary of some, and not necessarily all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, belong to the protection scope of the present invention.
Example 1
The water quality of the rare earth high-salinity wastewater in the embodiment is as follows: pH is 3-10, COD is 1000mg/L-5000mg/L,
the salt content is 50-200g/L, BOD is about 400-2000mg/L, and SS is 100-1000 mg/L.
The method for removing COD from the rare earth high-salinity wastewater comprises the following steps:
(1) pretreatment and oil removal: and (3) the high-salinity wastewater enters a pretreatment oil removal unit to remove non-soluble grease in the wastewater, and the obtained wastewater enters the step (2) to be treated after passing through the pretreatment oil removal unit.
(2) Desalting and deaminating: and (2) desalting the effluent in the step (1) by adopting an alkali-added steam stripping rectification deamination method, adding calcium salt compounded by calcium hydroxide, calcium carbonate, calcium chloride, calcium oxide and sodium hydroxide with the content ratio of calcium to sulfate radical of 1-5: 1, stirring for reaction for 10-30 min, precipitating and filtering, wherein the salt content is 10-20g/L, and feeding the clear liquid into the next stage. The volatilized ammonia gas can be recovered through an ammonia gas absorption system, and the recovered ammonia water can return to the rare earth non-ferrous extraction system. The pH value of the effluent is adjusted to 6-8, and the effluent enters a biochemical unit.
(3) Biochemical COD removal: and (3) the desalted wastewater in the step (2) enters a biochemical unit, and most of COD is removed through degradation of domesticated activated sludge. Domestication of activated sludge, preparing simulated wastewater, wherein the components of the simulated wastewater comprise 1-2g/L of glucose, 0.01-0.1g/L of sodium phosphate, 0.01-0.1g/L of monopotassium phosphate, 0.01-0.1g/L of calcium chloride, 0.01-0.1g/L of magnesium sulfate and 0.01-0.02g/L of ferrous sulfate, mixing the simulated wastewater with the wastewater to prepare simulated wastewater with different proportions, domesticating the activated sludge, wherein the domestication period is 20 days, and after stable operation, the removal rate of COD is more than 80%.
(4) Deep treatment: and (4) the biochemical effluent in the step (3) enters an ozone catalytic oxidation unit for advanced treatment, and the effluent is within 60mg/L and finally reaches the standard to be discharged.
Example 2
The quality of the colored high-salinity wastewater in the implementation is as follows: pH is 6-9, COD is 1000mg/L-3000mg/L,
the salt content is 50-100g/L, BOD is about 400-1200mg/L, and SS is 100-1000 mg/L.
The method for removing COD from the colored high-salinity wastewater comprises the following steps:
(1) pretreatment and oil removal: and (3) the high-salinity wastewater enters a pretreatment oil removal unit to remove non-soluble grease in the wastewater, and the obtained wastewater enters the step (2) to be treated after passing through the pretreatment oil removal unit.
(2) Desalting and deaminating: and (2) desalting the effluent in the step (1) by adopting an alkali-added steam stripping rectification deamination method, adding calcium salt compounded by calcium hydroxide, calcium carbonate, calcium chloride, calcium oxide and sodium hydroxide with the content ratio of calcium to sulfate radical of 1-4: 1, stirring for reaction for 10-30 min, precipitating and filtering, wherein the salt content is 10-20g/L, and feeding the clear liquid into the next stage. The volatilized ammonia gas can be recovered through an ammonia gas absorption system, and the recovered ammonia water can return to the rare earth non-ferrous extraction system. The pH value of the effluent is adjusted to 6-8, and the effluent enters a biochemical unit.
(3) Biochemical COD removal: and (3) the desalted wastewater in the step (2) enters a biochemical unit, and most of COD is removed through degradation of domesticated activated sludge. Domestication of activated sludge, preparing simulated wastewater, wherein the components of the simulated wastewater comprise 1-2g/L of glucose, 0.01-0.1g/L of sodium phosphate, 0.01-0.1g/L of monopotassium phosphate, 0.01-0.1g/L of calcium chloride, 0.01-0.1g/L of magnesium sulfate and 0.01-0.02g/L of ferrous sulfate, mixing the simulated wastewater with the wastewater to prepare simulated wastewater with different proportions, domesticating the activated sludge, wherein the domestication period is one month, and after stable operation, the removal rate of COD is more than 80%.
(4) Deep treatment: and (4) the biochemical effluent in the step (3) enters an ozone catalytic oxidation unit for advanced treatment, and the effluent is within 60mg/L and finally reaches the standard to be discharged.
Example 3
The water quality of the rare earth high-salinity wastewater in the embodiment is as follows: pH is 5-10, COD is 1000mg/L-2000mg/L,
the salt content is 50-80g/L, BOD is about 400-800mg/L, and SS is 100-1000 mg/L.
The method for removing COD from the rare earth high-salinity wastewater comprises the following steps:
(1) pretreatment and oil removal: and (3) the high-salinity wastewater enters a pretreatment oil removal unit to remove non-soluble grease in the wastewater, and the obtained wastewater enters the step (2) to be treated after passing through the pretreatment oil removal unit.
(2) Desalting and deaminating: and (2) desalting the effluent in the step (1) by adopting an alkali-added steam stripping rectification deamination method, adding calcium salt compounded by calcium hydroxide, calcium carbonate, calcium chloride, calcium oxide and sodium hydroxide with the content ratio of calcium to sulfate radical of 1-3: 1, stirring for reaction for 10-30 min, precipitating and filtering, wherein the salt content is 10-20g/L, and feeding the clear liquid into the next stage. The volatilized ammonia gas can be recovered through an ammonia gas absorption system, and the recovered ammonia water can return to the rare earth non-ferrous extraction system. The pH value of the effluent is adjusted to 6-8, and the effluent enters a biochemical unit.
(3) Biochemical COD removal: and (3) the desalted wastewater in the step (2) enters a biochemical unit, and most of COD is removed through degradation of domesticated activated sludge. Domestication of activated sludge, preparing simulated wastewater, wherein the components of the simulated wastewater comprise 1-2g/L of glucose, 0.01-0.1g/L of sodium phosphate, 0.01-0.1g/L of monopotassium phosphate, 0.01-0.1g/L of calcium chloride, 0.01-0.1g/L of magnesium sulfate and 0.01-0.02g/L of ferrous sulfate, mixing the simulated wastewater with the wastewater to prepare simulated wastewater with different proportions, domesticating the activated sludge, wherein the domestication period is 40 days, and after stable operation, the removal rate of COD is more than 80%.
(4) Deep treatment: and (4) the biochemical effluent in the step (3) enters an ozone catalytic oxidation unit for advanced treatment, and the effluent is within 60mg/L and finally reaches the standard to be discharged.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention. The scope of the invention is defined by the claims and their equivalents.
Claims (10)
1. A system for treating high-salinity high-COD wastewater generated in rare earth or nonferrous smelting is characterized by comprising a pretreatment oil removal unit, a desalination and deamination unit, a sludge microorganism domestication unit, a biochemical treatment unit and a high-grade oxidation treatment unit; the outlet of the pretreatment oil removal unit is connected with the inlet of the desalination and deamination unit; the outlet of the desalting and deamination unit and the outlet of the sludge microorganism domestication unit are connected with the inlet of the biochemical treatment unit; the outlet of the biochemical treatment unit is connected with the inlet of the advanced oxidation treatment unit.
2. The system of claim 1, wherein the rare earth or non-ferrous smelting high salt high COD wastewater is characterized by: pH value is 5-10, COD is 2000-4 2-Is 50-200g/L, NH4 +Is 400g/L for 100-.
3. The system of claim 1, wherein the pre-treatment oil removal unit comprises a coalescing oil removal device, an activated carbon oil removal device, and a filtration oil removal device.
4. The system of claim 1, wherein the desalination and deamination unit comprises a calcium salt dosing device and an ammonia gas absorption device; preferably, the calcium salt is a calcium salt compounded by calcium hydroxide, calcium carbonate, calcium chloride, calcium oxide and sodium hydroxide.
5. The system of claim 1, wherein the sludge microorganism acclimation unit comprises a plurality of microorganism culture devices, culture solution and wastewater with different proportions are added into the microorganism culture devices; preferably, the culture solution comprises the following components: 1-2g/L glucose, 0.01-0.1g/L sodium phosphate, 0.01-0.1g/L potassium dihydrogen phosphate, 0.01-0.1g/L calcium chloride, 0.01-0.1g/L magnesium sulfate and 0.01-0.02g/L ferrous sulfate; preferably, the strain of the sludge microorganism comes from the bottom sediment of the sewage outlet of the smelting wastewater and is obtained by separation and purification means.
6. The system of claim 1, wherein the biochemical treatment unit comprises a domesticated sludge microorganism dosing device and an aeration device; preferably, the aeration device is an aeration disc, and the aeration quantity ensures that the oxygen content of the water body is 1-4 mg/L.
7. The system of claim 6, wherein the advanced oxidation unit comprises an ozone source, an ozone aeration device, and an ozone off-gas destruction device; preferably, the ozone tail gas destruction device is connected with an aeration device of the biochemical treatment unit, and oxygen generated after the ozone tail gas is destroyed enters the biochemical treatment unit for aeration.
8. The method for treating the rare earth or nonferrous smelting high-salt high-COD wastewater by using the system of any one of claims 1 to 7 comprises the following steps:
the wastewater enters a pretreatment oil removal unit for treatment, and the dangerous waste generated by pretreatment oil removal is subjected to centralized treatment;
(2) the pretreated and deoiled wastewater enters a desalting and deaminating unit, calcium salt is added according to the molar ratio of calcium to sulfate radical of 1-5: 1, the mixture is stirred and reacted for 10-30 min, precipitation and filtration are carried out, and the pH value of filtrate is adjusted to 6-8; recovering the volatilized ammonia gas through an ammonia gas absorption device;
(3) acclimating the sludge microorganisms by a sludge microorganism acclimation unit with an acclimation period of 20-40 days;
(4) the filtrate obtained after the pH value is adjusted in the step (2) and the sludge microorganisms domesticated in the step (3) enter a biochemical treatment unit for treatment;
(5) and (4) discharging water from the biochemical treatment unit, and entering an ozone catalytic oxidation unit for advanced treatment.
9. The method according to claim 8, wherein the salt content of the filtrate in step (2) is 10-20 g/L.
10. The method according to claim 8, wherein the COD value of the biochemical treatment unit in the step (4) is reduced by more than 80%, and the COD value of the final effluent in the step (5) is below 60 mg/L.
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