CN114212914B - Petrochemical wastewater recycling method and system - Google Patents
Petrochemical wastewater recycling method and system Download PDFInfo
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- CN114212914B CN114212914B CN202111529001.1A CN202111529001A CN114212914B CN 114212914 B CN114212914 B CN 114212914B CN 202111529001 A CN202111529001 A CN 202111529001A CN 114212914 B CN114212914 B CN 114212914B
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/30—Electrical regeneration
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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- 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
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a petrochemical wastewater recycling method and system. The method comprises the following steps: (1) Feeding raw petrochemical wastewater into a regulating tank device, and regulating the water quality and water quantity by using the regulating tank; (2) The effluent of the regulating tank enters a degreasing tank through a lifting pump, compressed air and a degreasing agent are added, and oil substances are removed; (3) The effluent of the oil removal tank enters a neutralization coagulating sedimentation tank, quick lime, naOH, flocculating agents PAC and PAM are added, and AlCl is removed 3 、BF 3 Substances such as suspended matters, colloid and the like, filtering out solid substances, and then filtering out water to enter an intermediate water tank; (4) The lift pump sends the filtered water of the middle water tank into the precise filter to remove residual nonionic impurities and partial ionic substances, and the filtered water is used as pretreatment for advanced treatment; (5) The water treated by the precision filter enters a membraneless electrodeionization device to remove heavy metal plasma substances remained in the wastewater, and the clean water after treatment meets the recycling requirement.
Description
Technical Field
The invention relates to the field of petrochemical wastewater treatment, in particular to a method and a system for advanced treatment of petrochemical wastewater.
Background
The petrochemical industry is a national pillar industry, and can produce chemical raw materials such as ethylene, propylene, benzene and the like, synthetic plastics, rubber, resin and the like, however, a large amount of wastewater can be produced in the petrochemical production process. On the other hand, BF is widely used in petrochemical industry 3 、AlCl 3 Acid catalysts such as nickel, copper, manganese and other metal catalysts, and the like, cause heavy metals and acidic substances to be contained in petrochemical wastewater. Such as improper treatment, would pose a significant threat to aquatic ecology and human health. The current method for treating petrochemical wastewater containing heavy metals mainly comprises a chemical precipitation method, a biochemical method, a high-grade oxidation method and the like, wherein the chemical precipitation method is simple to operate, but effluent is difficult to meet the discharge requirement, and needs to be treated by combining with other technologies; the treated effluent can reach the discharge standard by a biochemical method, but heavy metals can cause microbial poisoning and cause system failure; the advanced oxidation method can effectively remove organic matters, but the heavy metal removal effect is poor, and the treated water is difficult to recycle.
The existing electrodeionization technology can realize in-situ electroregeneration of resin, but an ion exchange membrane is needed, and the ion exchange membrane is expensive and is easy to cause problems of scaling, pollution and concentration polarization.
Membrane-free electrodeionization is a process that relies on electrolysis and water splitting to produce H + And OH (OH) - Treatment/electrical regeneration process of regenerated ion exchange resins. Compared with the traditional electrodeionization technology, the membraneless electrodeionization technology does not need to use an ion exchange membrane, and has the advantages of simple structure, difficult polarization scaling, convenient disassembly and assembly and the like.
However, in the prior art, the effect is not ideal when the traditional resin layer structure is filled in the membraneless electrodeionization system to treat heavy metal wastewater, and OH is generated in the process of electric regeneration - Hydroxide precipitates are formed with heavy metal ions, so that resin channels are blocked; on the other hand, the filled resin is poor in conductivity, and the regeneration efficiency of the resin is often affected. And in the prior art, no membraneless electrodeionization system is applied to the case of treating petrochemical wastewater.
In order to overcome the problems in the background art, the invention aims to provide a petrochemical wastewater recycling method and system, which can effectively remove heavy metals and recycle wastewater.
Disclosure of Invention
The invention aims to provide a petrochemical wastewater recycling method and system, which can effectively adsorb heavy metal ions, avoid hydroxide precipitation, improve the conductivity of a resin layer and improve the regeneration efficiency of resin.
The invention is realized by the following scheme: the system comprises an adjusting tank, an oil removal tank, a coagulating sedimentation tank, a first-stage filtering device, a precision filter and a membraneless electrodeionization device, wherein the adjusting tank, the oil removal tank, the coagulating sedimentation tank, the first-stage filtering device, the precision filter and the membraneless electrodeionization device are sequentially connected by pipelines, a lifting pump is further arranged between the adjusting tank and the oil removal tank, and a lifting pump is further arranged between the coagulating sedimentation tank and the precision filter; the membraneless electrodeionization device is filled with chelating cationic resin, strong acid cationic resin and weak acid cationic resin; the upper end of the membraneless electrodeionization device is an anode, and the lower end is a cathode.
Furthermore, a pair of anode and cathode electrodes are arranged at two ends of the resin layer in the membraneless electrodeionization device, and the anode and cathode electrodes are platinized titanium electrodes.
Further, the mixing volume ratio of the chelating cationic resin, the strong acid cationic resin and the weak acid cationic resin is chelate resin, wherein the ratio of the strong acid cationic resin to the weak acid cationic resin is=1-2:1-3:1-3, preferably, the chelate resin is strong acid cationic resin, the ratio of the weak acid cationic resin to the chelate resin is=1:1-2:1-3, and more preferably, the chelate resin is strong acid cationic resin, the ratio of the weak acid cationic resin is=1:1-1.5:1-2.
The invention also provides a petrochemical wastewater recycling method, which comprises the following steps: the method comprises the following steps:
(1) Feeding raw petrochemical wastewater into a regulating tank device, and regulating the water quality and water quantity by using the regulating tank;
(2) The effluent of the regulating tank enters a degreasing tank through a lifting pump, compressed air and a degreasing agent are added, after fully mixed and reacted through a stirrer, the oil substances are carried and floated by micro-bubbles, stay for 25min, and the oil substances are removed;
(3) The effluent of the oil removal tank enters a neutralization coagulating sedimentation tank, and quicklime, naOH, flocculating agents PAC and PAM are added at the same time, and the quicklime and the NaOH can neutralize acid catalysts such as AlCl in the wastewater 3 And BF 3 The flocculant can effectively remove suspended matters, colloid, partial COD and oil pollutants through flocculation adsorption, quick lime and NaOH are added to adjust the pH of the wastewater to 8-9 according to the water quality condition of petrochemical wastewater, the addition amount of the flocculant PAC is 5-20mg/L, the addition amount of the PAM is 0.1-1mg/L, the precipitated effluent enters a primary filter, and filtered water enters an intermediate pond after filtering solid matters;
(4) The lift pump sends the filtered water of the middle water tank into the precise filter to remove residual nonionic impurities and partial ionic substances, and the filtered water is used as pretreatment for advanced treatment;
(5) The effluent treated by the precision filter enters a membraneless electrodeionization device, residual heavy metal plasma substances in the wastewater are effectively removed through resin adsorption and electric regeneration, and the clean water after treatment meets the recycling requirement.
Further, in the step (3), quicklime and NaOH are added to adjust the pH of the wastewater to 8-9, the adding amount of the flocculating agent PAC is 5-20mg/L, and the adding amount of the PAM is 0.1-1mg/L.
The invention uses neutralization coagulating sedimentation as primary treatment, precise filtration as secondary treatment, and membraneless electrodeionization technique as tertiary treatment, thereby realizing effective removal of heavy metals and purification of wastewater, and the concentration of heavy metals after treatment is less than 0.1mg/L, and the conductivity of effluent is less than 3us/cm.
Furthermore, the petrochemical wastewater treated by the method can be recycled, the concentration of nickel ions in the effluent is 0.01-0.08 mg/L, the concentration of copper ions is 0.02-0.10 mg/L, and the conductivity is 1-2 us/cm.
Further, the precise filter is filled with an ultrafiltration membrane or a nanofiltration membrane or a combination of the ultrafiltration membrane and the nanofiltration membrane.
Further, the membraneless electrodeionization device is filled with chelate resin, strong acid resin and weak acid resin, wherein the mixing ratio of the chelate resin to the strong acid resin to the weak acid resin=1-2:1-3:1-3. Preferably, the chelate resin is a strong acid positive resin and a weak acid positive resin=1:1 to 2:1 to 3, and more preferably, the chelate resin is a strong acid positive resin and a weak acid positive resin=1:1 to 1.5:1 to 2. The resin filling mode can effectively adsorb heavy metal ions, avoid hydroxide precipitation, improve the conductivity of a resin layer and improve the regeneration efficiency of the resin.
Furthermore, a pair of anode and cathode electrodes are arranged at two ends of a resin layer in the membraneless electrodeionization device, the electrodes are platinized titanium electrodes, isopropanol is used as a solvent, chloroplatinic acid is used as a precursor solution, 1 part of chloroplatinic acid is dissolved in 8-50 parts of isopropanol, a titanium mesh is used as a matrix, and the membraneless electrodeionization device is prepared by a high-temperature roasting method. Under the condition of electrifying, the platinized titanium electrode can effectively promote water electrolysis and water splitting reaction to generate H + And OH (OH) - And regenerating the failed resin to realize green treatment.
Further, the resin in the membraneless electrodeionization device adopts electric regeneration, the upper end is an anode, the lower end is a cathode, and the current density during regeneration is 100-350A/m 2 . The electrode can be placed in a manner that can effectively avoid the generation of hydroxide precipitation and prevent the failure of resin due to precipitation pollution. Preferably, the regeneration current density is 200-350A/m 2 。
Compared with the prior art, the invention has the following advantages:
1. the invention applies the membraneless electrodeionization technology to the petrochemical wastewater treatment field to realize heavy metal removal and wastewater recycling; research shows that the upper end of the membraneless electrodeionization device is connected with the anode, and the lower end of the membraneless electrodeionization device is connected with the cathode for regeneration, so that the generation of hydroxide precipitation can be effectively avoided, the pollution of resin is prevented, and the utilization rate of the resin is improved.
2. According to the invention, the chelating cationic resin, the strong acid cationic resin and the weak acid cationic resin are filled in the membraneless deionization device, so that heavy metal ions in wastewater are effectively removed, the generation of hydroxide precipitation is avoided, the conductivity of a resin layer is improved, the regeneration efficiency of the resin is improved, and continuous regeneration is realized.
3. The invention uses neutralization coagulating sedimentation as primary treatment, precise filtration as secondary treatment, and membraneless electrodeionization technology as tertiary treatment, thereby realizing the effective removal of heavy metals in petrochemical wastewater and purification of wastewater, and the concentration of heavy metals after treatment is less than 0.1mg/L, and the conductivity of effluent is less than 3us/cm, so that the petrochemical wastewater can be directly recycled.
4. The invention adopts a neutralization coagulating sedimentation method and a precise filter as pretreatment of the membraneless electrodeionization technology, thereby protecting the membraneless electrodeionization device, playing a double-insurance role on effluent and ensuring the quality of the effluent.
5. According to the invention, before neutralization and coagulation precipitation of petrochemical wastewater, the oil removal tank is arranged for oil removal treatment, so that oil substances can be effectively separated, and the oil substances can be recycled according to the needs.
6. The solution scheme adopted by the invention is suitable for purifying and recycling heavy metal-containing wastewater generated in petrochemical industry.
Drawings
FIG. 1 is a schematic diagram of the treatment method of the present invention.
The drawings are illustrated as follows:
the device comprises a 1-adjusting tank, a 2-oil removal tank, a 3-neutralization coagulating sedimentation tank, a 4-primary filtering device, a 5-intermediate water tank, a 6-precision filter, a 7-membraneless electrodeionization device, an 8-clean water tank, a 9-lifting pump, a 10-lifting pump and an 11-lifting pump.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the present invention. In addition, the technical features described below in the various embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
Copper-containing and nickel-containing wastewater generated by a certain C9 petroleum resin production enterprise is treated by adopting the method and the system, and the method comprises the following steps:
(1) Raw water enters a regulating tank device, and the water quality and water quantity are regulated by the regulating tank;
(2) The effluent of the regulating tank enters a degreasing tank through a lifting pump, compressed air and a degreasing agent are added, after fully mixed and reacted through a stirrer, the oil substances are carried and floated by micro-bubbles, stay for 25min, and the oil substances are removed;
(3) The effluent of the oil removal tank enters a neutralization coagulation sedimentation tank, quick lime and NaOH are added to adjust the pH to 8.5-9, a flocculating agent PAC 10-18mg/L and PAM 0.4-0.8mg/L are added, the effluent after sedimentation enters a primary filter, and filtered water enters an intermediate water tank after solid substances are filtered;
(4) The lift pump sends the filtered water of the middle water tank into the precise filter to remove residual nonionic impurities and partial ionic substances, and the filtered water is used as pretreatment for advanced treatment;
(5) The water treated by the precision filter enters a membraneless electrodeionization device, three resins in the device are mixed and filled, the mixing proportion is chelate resin, strong acid positive resin and weak acid positive resin=1:1-2:1-3, and the treatment is just like a common ion exchange process; the concentration of nickel ions in the treated effluent is 0.01-0.08 mg/L, the concentration of copper ions is 0.02-0.10 mg/L, and the conductivity is 1-2 us/cm.
After the mixed resin is continuously treated for 60-76 hours, the resin begins to lose efficacy and the water quality requirement of the effluent is not met; then high-voltage electric regeneration is adopted, the regeneration time is 30min, and the regeneration current density is 200-350A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the After regeneration, the resin performance is recovered, the resin starts to lose efficacy after 150-300min of adsorption treatment, and then electric regeneration-adsorption treatment is carried out, and no sediment is generated after each regeneration.
Example 2
Copper-containing and nickel-containing wastewater generated by a certain C9 petroleum resin production enterprise is treated by adopting the method and the system, and the method comprises the following steps:
(1) Raw water enters a regulating tank device, and the water quality and water quantity are regulated by the regulating tank;
(2) The effluent of the regulating tank enters a degreasing tank through a lifting pump, compressed air and a degreasing agent are added, after fully mixed and reacted through a stirrer, the oil substances are carried and floated by micro-bubbles, stay for 25min, and the oil substances are removed;
(3) The effluent of the oil removal tank enters a neutralization coagulation sedimentation tank, quick lime and NaOH are added to adjust the pH to 8.5, a flocculating agent PAC 10mg/L and PAM 0.4mg/L are added, the effluent after sedimentation enters a primary filter, and filtered water enters an intermediate water tank after solid substances are filtered;
(4) The lift pump sends the filtered water of the middle water tank into the precise filter to remove residual nonionic impurities and partial ionic substances, and the filtered water is used as pretreatment for advanced treatment;
(5) The treated effluent of the precision filter enters a membraneless electrodeionization device, three resins in the device are mixed and filled, the mixing ratio is chelate resin, strong acid positive resin and weak acid positive resin=1:2:1, and the treatment is just like a common ion exchange process; the concentration of nickel ions in the treated effluent is 0.02mg/L, the concentration of copper ions is 0.02mg/L, and the conductivity is 1.3us/cm.
After the mixed resin is continuously treated for 73 hours, the resin begins to lose efficacy and the water quality requirement of the effluent is not met; then high-voltage electric regeneration is adopted, the regeneration time is 30min, and the regeneration current density is 200A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the After regeneration, the resin properties were recovered, and the resin adsorption treatment was started to fail after 150 minutes, and then the electro-regeneration-adsorption treatment was performed. The resin had no precipitate after each regeneration.
Example 3
Copper-containing and nickel-containing wastewater generated by a certain C9 petroleum resin production enterprise is treated by adopting the method and the system, and the method comprises the following steps:
(1) Raw water enters a regulating tank device, and the water quality and water quantity are regulated by the regulating tank;
(2) The effluent of the regulating tank enters a degreasing tank through a lifting pump, compressed air and a degreasing agent are added, after fully mixed and reacted through a stirrer, the oil substances are carried and floated by micro-bubbles, stay for 25min, and the oil substances are removed;
(3) The effluent of the oil removal tank enters a neutralization coagulation sedimentation tank, quick lime and NaOH are added to adjust the pH to 8.6, a flocculating agent PAC 15mg/L and PAM 0.6mg/L are added, the effluent after sedimentation enters a primary filter, and filtered water enters an intermediate water tank after solid substances are filtered;
(4) The lift pump sends the filtered water of the middle water tank into the precise filter to remove residual nonionic impurities and partial ionic substances, and the filtered water is used as pretreatment for advanced treatment;
(5) The treated effluent of the precision filter enters a membraneless electrodeionization device, three resins in the device are mixed and filled, the mixing proportion is chelate resin, strong acid positive resin and weak acid positive resin=1:1.2:2, and the treatment is just like a common ion exchange process; the concentration of nickel ions in the treated effluent is 0.05mg/L, the concentration of copper ions is 0.08mg/L, and the conductivity is 1.5us/cm.
After the mixed resin is continuously treated for 60 hours, the resin begins to lose efficacy and the water quality requirement of the effluent is not met; then high-voltage electric regeneration is adopted, the regeneration time is 30min, and the regeneration current density is 250A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the After regeneration, the resin properties were recovered, and the resin adsorption treatment was started to fail after 190 minutes, and then the electro-regeneration-adsorption treatment was performed. The resin had no precipitate after each regeneration.
Example 4
Copper-containing and nickel-containing wastewater generated by a certain C9 petroleum resin production enterprise is treated by adopting the method and the system, and the method comprises the following steps:
(1) Raw water enters a regulating tank device, and the water quality and water quantity are regulated by the regulating tank;
(2) The effluent of the regulating tank enters a degreasing tank through a lifting pump, compressed air and a degreasing agent are added, after fully mixed and reacted through a stirrer, the oil substances are carried and floated by micro-bubbles, stay for 25min, and the oil substances are removed;
(3) The effluent of the oil removal tank enters a neutralization coagulation sedimentation tank, quick lime and NaOH are added to adjust the pH to 9, a flocculating agent PAC 18mg/L and PAM 0.8mg/L are added, the effluent after sedimentation enters a primary filter, and filtered water enters an intermediate water tank after solid substances are filtered;
(4) The lift pump sends the filtered water of the middle water tank into the precise filter to remove residual nonionic impurities and partial ionic substances, and the filtered water is used as pretreatment for advanced treatment;
(5) The treated effluent of the precision filter enters a membraneless electrodeionization device, three resins in the device are mixed and filled, the mixing proportion is chelate resin, strong acid positive resin and weak acid positive resin=1:1.5:3, and the treatment is just like a common ion exchange process; the concentration of nickel ions in the treated effluent is 0.07mg/L, the concentration of copper ions is 0.10mg/L, and the conductivity is 2.0us/cm.
After the mixed resin is continuously treated for 61 hoursThe resin begins to fail, and the water quality requirement of the effluent is not met; then high-voltage electric regeneration is adopted, the regeneration time is 30min, and the regeneration current density is 200A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the After regeneration, the resin properties were recovered, and the resin adsorption treatment started to fail after 178 minutes, and then the electro-regeneration-adsorption treatment was performed. The resin had no precipitate after each regeneration.
Example 5
The difference from example 3 is that chelate resin: strong acid cation resin: weak acid cation resin=1:1.2:1, nickel ion concentration of treated effluent is 0.03mg/L, copper ion concentration is 0.04mg/L, conductivity is 1.0us/cm.
After the mixed resin is continuously treated for 76 hours, the resin begins to lose efficacy and the water quality requirement of the effluent is not met; then high-voltage electric regeneration is adopted, the regeneration time is 30min, and the regeneration current density is 350A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the After regeneration, the resin properties were recovered, and the resin adsorption treatment was started to fail after 280 minutes, and then the electro-regeneration-adsorption treatment was performed. The resin had no precipitate after each regeneration.
Comparative example 1
The difference from example 5 is that the strong acid cation resin is a weak acid cation resin=2.2:1, the nickel ion concentration of the effluent after petrochemical wastewater treatment is 0.86mg/L, and the copper ion concentration is 0.92mg/L.
After the mixed resin is continuously treated for 72 hours, the resin begins to lose efficacy and the water quality requirement of the effluent is not met; then high-voltage electric regeneration is adopted, the regeneration time is 30min, and the regeneration current density is 200A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the After regeneration, the resin adsorption treatment was started to fail after 100 minutes, and then the electro-regeneration-adsorption treatment was performed. The resin had precipitates after each regeneration and the time to continue use after each regeneration was gradually shortened.
Comparative example 2
The difference from example 5 is that the chelating resin is strong acid positive resin=2:1.2, and the nickel ion concentration of the treated effluent is 0.43mg/L and the copper ion concentration is 0.63mg/L.
After the mixed resin is continuously treated for 75 hours, the resin begins to lose efficacy and the water quality requirement of the effluent is not met; then high-voltage electric regeneration is adopted, the regeneration time is 30min, and the regeneration current density is 250A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the And thenAfter the regeneration, the resin properties were recovered, and the resin adsorption treatment was started to fail after 160 minutes, and then the electro-regeneration-adsorption treatment was performed. The resin had precipitates after each regeneration and the time to continue use after each regeneration was gradually shortened.
Comparative example 3
The difference from example 5 is that the chelating resin is weak acid positive resin=2.2:1, and the nickel ion concentration of the treated effluent is 0.21mg/L and the copper ion concentration is 0.24mg/L.
After the mixed resin is continuously treated for 65 hours, the resin begins to lose efficacy and the water quality requirement of the effluent is not met; then high-voltage electric regeneration is adopted, the regeneration time is 30min, and the regeneration current density is 270A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the After regeneration, the resin properties were recovered, and the resin adsorption treatment was started to fail after 200 minutes, and then the electro-regeneration-adsorption treatment was performed. The resin had precipitates after each regeneration and the time to continue use after each regeneration was gradually shortened.
The mixed resin conductivity, the first adsorption treatment period of the mixed resin, the electric regeneration efficiency (electric regeneration post-treatment period), whether precipitation is generated after electric regeneration, and the removal rate of metal ions in wastewater after regeneration in the membraneless electrodeionization device in the above examples and comparative examples were characterized, and specific data are shown in the following table 1:
table 1: characterization data for the resins of the examples.
From the above data characterization, it was found that the strong acid cationic resin of comparative example 1 was high in relative content and good in conductivity, and the resin utilization time after regeneration was 181 minutes under the regeneration condition of 350A current density, whereas in example 5, three kinds of mixed resins were used, although the conductivity was slightly poor, but the regeneration capability was strong, and the time utilized after electric regeneration was 280 minutes under the same current density regeneration condition. The conductivity and the electrical regeneration are both considered, and the metal ion removal rate is very high, and the adsorption performance is very good. And no precipitation occurs on the resin at the time of regeneration.
It will be readily understood by those skilled in the art that the foregoing description is merely illustrative of the presently preferred embodiments of the invention and is not intended to limit the invention to the particular forms disclosed, but to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The petrochemical wastewater recycling system comprises an adjusting tank, an oil removal tank, a coagulating sedimentation tank, a primary filtering device, a precise filter and a membraneless electrodeionization device, and is characterized in that the adjusting tank, the oil removal tank, the coagulating sedimentation tank, the primary filtering device, the precise filter and the membraneless electrodeionization device are sequentially connected by adopting pipelines, a lifting pump is further arranged between the adjusting tank and the oil removal tank, and a lifting pump is further arranged between the coagulating sedimentation tank and the precise filter; the membraneless electrodeionization device is filled with chelating cationic resin, strong acid cationic resin and weak acid cationic resin; the upper end of the membraneless electrodeionization device is an anode, the lower end of the membraneless electrodeionization device is a cathode, and the mixing volume ratio of the chelating positive resin, the strong acid positive resin and the weak acid positive resin is chelating resin, wherein the strong acid positive resin and the weak acid positive resin are respectively 1-2:1-3:1-3.
2. The system for recycling petrochemical wastewater according to claim 1, wherein a pair of anode and cathode electrodes are arranged at two ends of the resin layer in the membraneless electrodeionization device, and are platinized titanium electrodes.
3. The system for recycling petrochemical wastewater according to claim 1 or 2, wherein the mixing volume ratio of the chelating cationic resin, the strong acid cationic resin and the weak acid cationic resin is the chelating resin, the strong acid cationic resin and the weak acid cationic resin=1:1-2:1-3.
4. The system for recycling petrochemical wastewater according to claim 1 or 2, wherein the mixing volume ratio of the chelating cationic resin, the strong acid cationic resin and the weak acid cationic resin is the chelating resin, the strong acid cationic resin and the weak acid cationic resin=1:1-1.5:1-2.
5. A petrochemical wastewater recycling method is characterized in that: a method for treating petrochemical wastewater and recycling using the system of any one of claims 1-4, the method comprising the steps of:
(1) Feeding raw petrochemical wastewater into a regulating tank device, and regulating the water quality and water quantity by using the regulating tank;
(2) The effluent of the regulating tank enters a degreasing tank through a lifting pump, compressed air and a degreasing agent are added, after fully mixed and reacted through a stirrer, the oil substances are carried and floated by micro-bubbles, stay for 25min, and the oil substances are removed;
(3) The effluent of the oil removal tank enters a neutralization coagulation sedimentation tank, quick lime, naOH, flocculating agent PAC and PAM are added at the same time, the precipitated effluent enters a first-stage filter, and filtered water enters an intermediate water tank after filtering solid substances;
(4) The lift pump sends the filtered water of the middle water tank into the precise filter to remove residual nonionic impurities and partial ionic substances, and the filtered water is used as pretreatment for advanced treatment;
(5) The effluent treated by the precision filter enters a membraneless electrodeionization device, residual heavy metals in the wastewater are effectively removed through resin adsorption and electric regeneration, and the clean water after treatment meets the recycling requirement.
6. The method for recycling petrochemical wastewater according to claim 5, wherein the pH of the wastewater is adjusted to 8-9 by adding quicklime and NaOH in the step (3), the adding amount of the flocculating agent PAC is 5-20mg/L, and the adding amount of the PAM is 0.1-1mg/L.
7. The method for recycling petrochemical wastewater according to claim 5, wherein in the step (3), quicklime and NaOH are added to adjust the pH to 8.5-9, and a flocculating agent PAC 10-18mg/L and PAM 0.4-0.8mg/L are added.
8. The method for recycling petrochemical wastewater according to any one of claims 5-7, wherein the resin of the membraneless electrodeionization device in step (5) is a resin of a membraneless electrodeionization deviceElectric regeneration is adopted, and the regeneration current density is 100-350A/m 2 。
9. A method for recycling petrochemical wastewater according to any one of claims 5-7, wherein: the precise filter is filled with an ultrafiltration membrane or a nanofiltration membrane or a combination of the ultrafiltration membrane and the nanofiltration membrane.
10. A method for recycling petrochemical wastewater according to any one of claims 5-7, wherein: a pair of negative and positive electrodes are arranged at two ends of a resin layer in the membraneless electrodeionization device, and are platinized titanium electrodes; the preparation method of the platinized titanium electrode comprises the following steps: the method is characterized in that isopropanol is used as a solvent, chloroplatinic acid is used as a precursor liquid, 1 part of chloroplatinic acid is dissolved in 8-50 parts of isopropanol, a titanium mesh is used as a matrix, and a high-temperature roasting method is adopted to prepare the titanium mesh.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5500126A (en) * | 1994-10-20 | 1996-03-19 | Rohm And Haas Company | Process for removal of metal ions from aqueous solutions |
| JPH11179369A (en) * | 1997-12-24 | 1999-07-06 | Japan Organo Co Ltd | Electric deionized water producing apparatus |
| CN102583646A (en) * | 2012-01-19 | 2012-07-18 | 浙江大学 | Membraneless electrodeionization method and system thereof, capable of directly exhausting oxygen gas and hydrogen gas outwards are |
| CN104445535A (en) * | 2014-12-12 | 2015-03-25 | 浙江大学 | Screw rod pressing membraneless electrodeionization continuous water production system |
| CN111320243A (en) * | 2020-04-10 | 2020-06-23 | 浙江大学 | Membrane-free electrodeionization method and device with current perpendicular to water flow direction |
| CN112679001A (en) * | 2020-12-14 | 2021-04-20 | 大连平源环保科技有限公司 | Membrane-free electrodeionization continuous water production system based on equivalent filter elements |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3714076B2 (en) * | 1999-12-17 | 2005-11-09 | 栗田工業株式会社 | Fluorine-containing wastewater treatment apparatus and treatment method |
| US6929748B2 (en) * | 2003-03-28 | 2005-08-16 | Chemitreat Pte Ltd | Apparatus and method for continuous electrodeionization |
| JP2005238181A (en) * | 2004-02-27 | 2005-09-08 | Nippon Steel Corp | Method for treating wastewater to recover valuable metal and plating solution manufacturing method |
| JP4561967B2 (en) * | 2004-05-19 | 2010-10-13 | オルガノ株式会社 | Method and apparatus for recovering water from waste water containing tetraalkylammonium ions |
| CN103505905B (en) * | 2012-06-18 | 2016-12-21 | 天津天士力现代中药资源有限公司 | The method that chelating resin removes traditional Chinese medicine heavy metal with amberlite oil/fat composition |
| CN102815765B (en) * | 2012-08-30 | 2014-04-02 | 中国石油天然气股份有限公司 | Deep softening method of thick oil sewage |
| JP2014151310A (en) * | 2013-02-13 | 2014-08-25 | Toshiba Corp | Water treatment method and water treatment equipment |
| CN113307438A (en) * | 2021-06-30 | 2021-08-27 | 赛恩斯环保股份有限公司 | Treatment method of nickel-cobalt smelting heavy metal wastewater |
| CN114210374B (en) * | 2021-12-14 | 2023-08-18 | 宁波职业技术学院 | Ion exchange resin suitable for petrochemical wastewater treatment and preparation method thereof |
-
2021
- 2021-12-14 CN CN202111529001.1A patent/CN114212914B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5500126A (en) * | 1994-10-20 | 1996-03-19 | Rohm And Haas Company | Process for removal of metal ions from aqueous solutions |
| JPH11179369A (en) * | 1997-12-24 | 1999-07-06 | Japan Organo Co Ltd | Electric deionized water producing apparatus |
| CN102583646A (en) * | 2012-01-19 | 2012-07-18 | 浙江大学 | Membraneless electrodeionization method and system thereof, capable of directly exhausting oxygen gas and hydrogen gas outwards are |
| CN104445535A (en) * | 2014-12-12 | 2015-03-25 | 浙江大学 | Screw rod pressing membraneless electrodeionization continuous water production system |
| CN111320243A (en) * | 2020-04-10 | 2020-06-23 | 浙江大学 | Membrane-free electrodeionization method and device with current perpendicular to water flow direction |
| CN112679001A (en) * | 2020-12-14 | 2021-04-20 | 大连平源环保科技有限公司 | Membrane-free electrodeionization continuous water production system based on equivalent filter elements |
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