CN114212914A - Method and system for recycling petrochemical wastewater - Google Patents
Method and system for recycling petrochemical wastewater Download PDFInfo
- Publication number
- CN114212914A CN114212914A CN202111529001.1A CN202111529001A CN114212914A CN 114212914 A CN114212914 A CN 114212914A CN 202111529001 A CN202111529001 A CN 202111529001A CN 114212914 A CN114212914 A CN 114212914A
- Authority
- CN
- China
- Prior art keywords
- resin
- tank
- water
- enters
- effluent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method and a system for recycling petrochemical wastewater. The method comprises the following steps: (1) raw petrochemical wastewater enters a regulating reservoir device, and the water quality and the water quantity are regulated by utilizing a regulating reservoir; (2) the effluent of the regulating reservoir enters an oil removal tank through a lift pump, and compressed air and an oil removal agent are added to remove oil substances; (3) the effluent of the oil removing tank enters a neutralization coagulation sedimentation tank, quicklime, NaOH, flocculating agent PAC and PAM are added, and AlCl is removed3、BF3Filtering out solid matters, filtering water to enter an intermediate water tank; (4) the lift pump sends the filtered water of the middle water tank into a precision filter to remove residual nonionic impurities and partial ionic substances as pretreatment of advanced treatment; (5) precision filtrationEffluent treated by the device enters a membraneless electrodeionization device to remove residual heavy metal plasma substances in wastewater, and the treated clear water 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 the national pillar industry, can produce chemical raw materials such as ethylene, propylene, benzene and the like, and synthesize products such as plastics, rubber, resin and the like, however, a large amount of waste water is generated in the petrochemical production process. On the other hand, BF is widely used in petrochemical industry3、AlCl3And the like, and metal catalysts such as nickel, copper, manganese and the like, so that the petrochemical wastewater contains heavy metals and acidic substances. If the treatment is improper, the aquatic ecology and the human health are greatly threatened. The current methods for treating the heavy metal-containing petrochemical wastewater mainly comprise a chemical precipitation method, a biochemical method, an advanced oxidation method and the like, wherein the chemical precipitation method is simple to operate, but effluent water cannot meet the discharge requirement easily, and needs to be treated by combining with other technologies; effluent treated by a biochemical method can reach the standard and be discharged, 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 effluent is difficult to recycle.
The existing electrodeionization technology can realize in-situ electrical regeneration of resin, but an ion exchange membrane is needed, and the ion exchange membrane is expensive and is easy to cause the 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-A treatment/electrical regeneration process for regenerating 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 and scaling, convenient assembly and disassembly 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 generated in the process of electrical regeneration-Will form hydroxide precipitate with heavy metal ionsStarch, thereby blocking the resin passage; on the other hand, the filled resin has poor conductivity and may affect the regeneration efficiency of the resin. In the prior art, a membraneless electrodeionization system is not applied to treatment of petrochemical wastewater.
In order to overcome the problems in the background art, the invention aims to provide a method and a system for recycling petrochemical wastewater, which can effectively remove heavy metals and recycle wastewater.
Disclosure of Invention
The invention aims to provide a method and a system for recycling petrochemical wastewater, which can effectively adsorb heavy metal ions, avoid generation of hydroxide precipitates, improve the conductivity of a resin layer and improve the regeneration efficiency of the resin.
The invention is realized by the following scheme: the system comprises an adjusting tank, an oil removing tank, a coagulating sedimentation tank, a primary filtering device, a precision filter and a membraneless electrodeionization device, wherein the adjusting tank, the oil removing tank, the coagulating sedimentation tank, the primary filtering device, the precision filter and the membraneless electrodeionization device are sequentially connected by pipelines, a lifting pump is arranged between the adjusting tank and the oil removing tank, and a lifting pump is arranged between the coagulating sedimentation tank and the precision filter; the membrane-free electrodeionization device is filled with chelating cation resin, strong acid cation resin and weak acid cation resin; the upper end of the membraneless electrodeionization device is an anode, and the lower end of the membraneless electrodeionization device is a cathode.
Furthermore, a pair of cathode and anode electrodes, which are all platinum-plated titanium electrodes, are arranged at two ends of the resin layer in the membraneless electrodeionization device.
The volume ratio of the chelating resin to the strong acid cation resin to the weak acid cation resin is 1-2: 1-3, preferably 1: 1-2: 1-3, more preferably 1: 1-2: 1-3.
The invention also provides a method for recycling petrochemical wastewater, which comprises the following steps: the method comprises the following steps:
(1) raw petrochemical wastewater enters a regulating reservoir device, and the water quality and the water quantity are regulated by utilizing a regulating reservoir;
(2) the effluent of the regulating reservoir enters an oil removal tank through a lift pump, compressed air and an oil removal agent are added, after full mixing reaction through a stirrer, oil substances are carried by micro bubbles to float upwards, and stay for 25min, and the oil substances are removed;
(3) the effluent of the oil removing tank enters a neutralization coagulation sedimentation tank, and simultaneously quicklime, NaOH, flocculating agent PAC and PAM are added, and the quicklime and the NaOH can neutralize acid catalyst such as AlCl in the wastewater3And BF3The flocculant can effectively remove suspended matters, colloids, partial COD (chemical oxygen demand) and oil pollutants through flocculation adsorption, quicklime and NaOH are added to adjust the pH of the wastewater to be 8-9 according to the water quality condition of petrochemical wastewater, the adding amount of the flocculant PAC is 5-20mg/L, the adding amount of PAM is 0.1-1mg/L, the effluent enters a primary filter after precipitation, and the filtered water enters an intermediate water tank after solid matters are filtered;
(4) the lift pump sends the filtered water of the middle water tank into a precision filter to remove residual nonionic impurities and partial ionic substances as pretreatment of 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 treated clear water meets the recycling requirement.
Further, adding quicklime and NaOH to adjust the pH value of the wastewater to 8-9 in the step (3), wherein the adding amount of a flocculating agent PAC is 5-20mg/L, and the adding amount of PAM is 0.1-1 mg/L.
The invention takes neutralization coagulation sedimentation as primary treatment, precise filtration as secondary treatment and a membrane-free electrodeionization technology as tertiary treatment, realizes effective removal of heavy metals and purification of wastewater, and the concentration of the heavy metals is less than 0.1mg/L and the conductivity of effluent is less than 3us/cm after treatment.
Furthermore, the petrochemical wastewater treated by the method can be recycled, the concentration of nickel ions in 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 precision filter is filled with an ultrafiltration membrane or a nanofiltration membrane or a combination of the two.
Furthermore, the membraneless electrodeionization device is filled with chelating cation resin, strong acid cation resin and weak acid cation resin, and the mixing ratio of the chelating resin to the strong acid cation resin to the weak acid cation resin is 1-2: 1-3. Preferably, the ratio of the chelating resin to the strong acid cation resin to the weak acid cation resin is 1: 1-2: 1-3, and more preferably, the ratio of the chelating resin to the strong acid cation resin to the weak acid cation resin is 1: 1-1.5: 1-2. The resin filling mode can effectively adsorb heavy metal ions, simultaneously avoids the generation of hydroxide precipitation, can also improve the conductivity of the resin layer, and improves the regeneration efficiency of the resin.
Furthermore, a pair of cathode and anode electrodes are arranged at two ends of a resin layer in the membraneless electrodeionization device, the cathode and anode electrodes are all platinum-plated 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 a high-temperature roasting method is adopted for preparing the membrane-free electrodeionization device. Under the condition of electrification, the platinized titanium electrode can effectively promote water electrolysis and water cracking reaction to generate H+And OH-And regenerating the failed resin to realize green treatment.
Furthermore, 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/m2. The electrode is arranged in a mode that hydroxide precipitation can be effectively avoided, and the failure of resin due to precipitation pollution is prevented. Preferably, the regenerative current density is 200 to 350A/m2。
Compared with the prior art, the invention has the following advantages:
1. the invention applies the membraneless electrodeionization technology to the field of petrochemical wastewater treatment, and realizes heavy metal removal and wastewater reuse; research shows that the regeneration is carried out when the upper end of the membraneless electrodeionization device is connected with the anode and the lower end is connected with the cathode, so that the generation of hydroxide precipitates can be effectively avoided, resin pollution is prevented, and the utilization rate of resin is improved.
2. According to the invention, the non-membrane deionization device is filled with three mixed resins of chelating cation resin, strong acid cation resin and weak acid cation resin, so that heavy metal ions in the wastewater are effectively removed, the generation of hydroxide precipitate is avoided, the conductivity of the resin layer can be improved, the regeneration efficiency of the resin is improved, and continuous regeneration is realized.
3. The invention takes neutralization coagulation sedimentation as primary treatment, precise filtration as secondary treatment and a membraneless electrodeionization technology as tertiary treatment, realizes effective removal of heavy metal in petrochemical wastewater and purification of wastewater, and the concentration of the heavy metal after treatment is less than 0.1mg/L, the conductivity of effluent is less than 3us/cm, and the effluent can be directly recycled.
4. The invention adopts a neutralization coagulation sedimentation method and a precise filter as the pretreatment of the membraneless electrodeionization technology, thereby not only protecting the membraneless electrodeionization device, but also playing a double-insurance role on the effluent and ensuring the quality of the effluent.
5. Before the petrochemical wastewater is neutralized and coagulated and precipitated, the oil removal tank is arranged for oil removal treatment, so that oil substances can be effectively separated and can be recycled according to requirements.
6. The solution adopted by the invention is suitable for purifying and recycling the wastewater containing heavy metals generated in the petrochemical industry.
Drawings
FIG. 1 is a schematic view of the treatment method of the present invention.
The drawings illustrate the following:
1-regulating pool, 2-deoiling tank, 3-neutralization coagulation sedimentation tank, 4-primary filtering device, 5-intermediate water pool, 6-precision filter, 7-membraneless electrodeionization device, 8-clean water pool, 9-lift pump, 10-lift pump and 11-lift pump.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention. In addition, the technical features mentioned in the embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
Example 1
The method and the system for treating the waste water containing copper and nickel generated by a certain C9 petroleum resin production enterprise comprise the following steps:
(1) raw water enters a regulating tank device, and the water quality and the water quantity are regulated by utilizing a regulating tank;
(2) the effluent of the regulating reservoir enters an oil removal tank through a lift pump, compressed air and an oil removal agent are added, after full mixing reaction through a stirrer, oil substances are carried by micro bubbles to float upwards, and stay for 25min, and the oil substances are removed;
(3) the effluent of the oil removing tank enters a neutralization coagulation sedimentation tank, quicklime and NaOH are simultaneously added to adjust the pH value to 8.5-9, flocculating agents 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 matters are filtered;
(4) the lift pump sends the filtered water of the middle water tank into a precision filter to remove residual nonionic impurities and partial ionic substances as pretreatment of advanced treatment;
(5) the method comprises the following steps that effluent treated by a precision filter enters a membraneless electrodeionization device, three kinds of resin are mixed and filled in the device, the mixing ratio is 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 h, the resin begins to lose efficacy and cannot meet the effluent water quality requirement; then high-voltage electricity is adopted for regeneration, the regeneration time is 30min, and the regeneration current density is 200-350A/m2(ii) a After regeneration, the resin performance is recovered, the resin begins to lose efficacy after the resin adsorption treatment is carried out for 150-300min, and then the electrical regeneration-adsorption treatment is carried out, wherein no precipitate is generated after each regeneration of the resin.
Example 2
The method and the system for treating the waste water containing copper and nickel generated by a certain C9 petroleum resin production enterprise comprise the following steps:
(1) raw water enters a regulating tank device, and the water quality and the water quantity are regulated by utilizing a regulating tank;
(2) the effluent of the regulating reservoir enters an oil removal tank through a lift pump, compressed air and an oil removal agent are added, after full mixing reaction through a stirrer, oil substances are carried by micro bubbles to float upwards, and stay for 25min, and the oil substances are removed;
(3) the effluent of the oil removing tank enters a neutralization coagulation sedimentation tank, quicklime and NaOH are simultaneously added to adjust the pH value to 8.5, flocculating agents PAC 10mg/L and PAM 0.4mg/L are added, the effluent after sedimentation enters a primary filter, and the filtered water enters an intermediate water tank after solid matters are filtered;
(4) the lift pump sends the filtered water of the middle water tank into a precision filter to remove residual nonionic impurities and partial ionic substances as pretreatment of advanced treatment;
(5) the water treated by the precision filter enters a membraneless electrodeionization device, and the three resins in the device are mixed and filled in the device, wherein the mixing ratio of the chelating resin to the strong acid cation resin to the weak acid cation resin is 1:2:1, and the treatment process 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 1.3 us/cm.
After the mixed resin is continuously treated for 73 hours, the resin begins to lose efficacy and cannot meet the effluent water quality requirement; then high-voltage electricity is adopted for regeneration, the regeneration time is 30min, and the regeneration current density is 200A/m2(ii) a After regeneration, the resin performance is recovered, the resin begins to lose efficacy after adsorption treatment for 150min, and then electric regeneration-adsorption treatment is carried out. No precipitate was formed after each regeneration of the resin.
Example 3
The method and the system for treating the waste water containing copper and nickel generated by a certain C9 petroleum resin production enterprise comprise the following steps:
(1) raw water enters a regulating tank device, and the water quality and the water quantity are regulated by utilizing a regulating tank;
(2) the effluent of the regulating reservoir enters an oil removal tank through a lift pump, compressed air and an oil removal agent are added, after full mixing reaction through a stirrer, oil substances are carried by micro bubbles to float upwards, and stay for 25min, and the oil substances are removed;
(3) the effluent of the oil removing tank enters a neutralization coagulation sedimentation tank, quicklime and NaOH are simultaneously added to adjust the pH value to 8.6, flocculating agents PAC 15mg/L and PAM 0.6mg/L are added, the effluent after sedimentation enters a primary filter, and the filtered water enters an intermediate water tank after solid matters are filtered;
(4) the lift pump sends the filtered water of the middle water tank into a precision filter to remove residual nonionic impurities and partial ionic substances as pretreatment of advanced treatment;
(5) the water treated by the precision filter enters a membraneless electrodeionization device, and the three resins in the device are mixed and filled in the device according to the mixing ratio of 1:1.2:2, namely the chelating resin, the strong acid cation resin and the weak acid cation resin, and the treatment is just like the 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 1.5 us/cm.
After the mixed resin is continuously treated for 60 hours, the resin begins to lose efficacy and cannot meet the effluent water quality requirement; then high-voltage electricity is adopted for regeneration, the regeneration time is 30min, and the regeneration current density is 250A/m2(ii) a And after regeneration, the resin performance is recovered, the resin begins to lose efficacy after adsorption treatment for 190min, and then electric regeneration-adsorption treatment is carried out. No precipitate was formed after each regeneration of the resin.
Example 4
The method and the system for treating the waste water containing copper and nickel generated by a certain C9 petroleum resin production enterprise comprise the following steps:
(1) raw water enters a regulating tank device, and the water quality and the water quantity are regulated by utilizing a regulating tank;
(2) the effluent of the regulating reservoir enters an oil removal tank through a lift pump, compressed air and an oil removal agent are added, after full mixing reaction through a stirrer, oil substances are carried by micro bubbles to float upwards, and stay for 25min, and the oil substances are removed;
(3) the effluent of the oil removing tank enters a neutralization coagulation sedimentation tank, quicklime and NaOH are simultaneously added to adjust the pH value to 9, flocculating agents PAC 18mg/L and PAM 0.8mg/L are added, the effluent after sedimentation enters a primary filter, and the filtered water enters an intermediate water tank after solid matters are filtered;
(4) the lift pump sends the filtered water of the middle water tank into a precision filter to remove residual nonionic impurities and partial ionic substances as pretreatment of advanced treatment;
(5) the water treated by the precision filter enters a membraneless electrodeionization device, and the three resins in the device are mixed and filled in the device according to the mixing ratio of 1:1.5:3, namely the chelating resin, the strong acid cation resin and the weak acid cation resin, and the treatment is just like the 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 2.0 us/cm.
After the mixed resin is continuously treated for 61 hours, the resin begins to lose efficacy and cannot meet the effluent water quality requirement; then high-voltage electricity is adopted for regeneration, the regeneration time is 30min, and the regeneration current density is 200A/m2(ii) a And after regeneration, the resin performance is recovered, the resin begins to lose efficacy after adsorption treatment for 178min, and then electric regeneration-adsorption treatment is carried out. No precipitate was formed after each regeneration of the resin.
Example 5
The difference from the example 3 is that the chelating resin, the strong acid cation resin and the weak acid cation resin are 1:1.2:1, the concentration of nickel ions in effluent after treatment is 0.03mg/L, the concentration of copper ions is 0.04mg/L, and the electric conductivity is 1.0 us/cm.
After the mixed resin is continuously treated for 76 hours, the resin begins to lose efficacy and cannot meet the effluent water quality requirement; then high-voltage electricity is adopted for regeneration, the regeneration time is 30min, and the regeneration current density is 350A/m2(ii) a After regeneration, the resin performance is recovered, the resin begins to lose efficacy after the adsorption treatment for 280min, and then the electric regeneration-adsorption treatment is carried out. No precipitate was formed after each regeneration of the resin.
Comparative example 1
The difference from the example 5 is that the ratio of the strong acid cation resin to the weak acid cation resin is 2.2:1, the concentration of nickel ions in effluent after the petrochemical wastewater treatment is 0.86mg/L, and the concentration of copper ions is 0.92 mg/L.
After the mixed resin is continuously treated for 72 hours, the resin begins to lose efficacy and cannot meet the effluent water quality requirement; then high-voltage electricity is adopted for regeneration, the regeneration time is 30min, and the regeneration current density is 200A/m2(ii) a After regeneration, the resin starts to lose efficacy after adsorption treatment for 100min, and then electric regeneration-adsorption treatment is carried out. 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 the example 5 lies in that the chelating resin is strong acid cation resin which is 2:1.2, the concentration of nickel ions in effluent water is 0.43mg/L, and the concentration of copper ions is 0.63mg/L after the treatment.
After the mixed resin is continuously treated for 75 hours, the resin begins to lose efficacy and cannot meet the effluent water quality requirement; then high-voltage electricity is adopted for regeneration, the regeneration time is 30min, and the regeneration current density is 250A/m2(ii) a And after regeneration, the resin performance is recovered, the resin begins to lose efficacy after adsorption treatment for 160min, and then electric regeneration-adsorption treatment is carried out. 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 the example 5 lies in that the chelating resin and the weak acid cation resin are 2.2:1, and the concentration of nickel ions and the concentration of copper ions in effluent water are 0.21mg/L and 0.24mg/L respectively after the treatment.
After the mixed resin is continuously treated for 65 hours, the resin begins to lose efficacy and cannot meet the effluent water quality requirement; then high-voltage electricity is adopted for regeneration, the regeneration time is 30min, and the regeneration current density is 270A/m2(ii) a After regeneration, the resin performance is recovered, the resin begins to lose efficacy after adsorption treatment for 200min, and then electric regeneration-adsorption treatment is carried out. The resin had precipitates after each regeneration and the time to continue use after each regeneration was gradually shortened.
The conductivity of the mixed resin in the membraneless electrodeionization device, the first adsorption treatment time of the mixed resin, the electrical regeneration efficiency (treatment time after electrical regeneration), whether the precipitate is generated after electrical regeneration and the removal rate of metal ions in wastewater after regeneration in the above examples and comparative examples are characterized, and the specific data are shown in the following table 1:
table 1: data for performance characterization of the resins of the examples.
According to the data representation, the strong acid cation resin in the comparative example 1 has high relative content and good conductivity, and the resin utilization time after regeneration under the regeneration condition of 350A current density is 181 minutes, while the three mixed resins in the example 5 have poor conductivity but strong regeneration capability, and the resin utilization time after electrical regeneration reaches 280 minutes under the same current density regeneration condition. The conductive material has both conductivity and electrical reproducibility, has high removal rate of metal ions, and has good adsorption performance. And no precipitation on the resin occurs upon regeneration.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of this invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of this invention should be included within the scope of protection of this invention.
Claims (10)
1. The utility model provides a system for petrochemical industry waste water recycle, contains equalizing basin, deoiling jar, coagulating sedimentation tank, one-level filter equipment, precision filter and no membrane electrodeionization device, its characterized in that: the device comprises an adjusting tank, an oil removal tank, a coagulating sedimentation tank, a primary filtering device, a precision filter and a membraneless electrodeionization device which are sequentially connected by pipelines, wherein a lifting pump is arranged between the adjusting tank and the oil removal tank, and a lifting pump is arranged between the coagulating sedimentation tank and the precision filter; the membrane-free electrodeionization device is filled with chelating cation resin, strong acid cation resin and weak acid cation resin; the upper end of the membraneless electrodeionization device is an anode, and the lower end of the membraneless electrodeionization device is a cathode.
2. The system according to claim 1, wherein a pair of cathode and anode electrodes, both of which are platinized titanium electrodes, are disposed at both ends of the resin layer in the membraneless electrodeionization device.
3. The system for recycling petrochemical wastewater according to claim 1 or 2, wherein the volume ratio of the chelating resin to the strong acid cation resin to the weak acid cation resin is 1-2: 1-3, preferably 1: 1-2: 1-3, more preferably 1: 1-1.5: 1-2.
4. A method for recycling petrochemical wastewater is characterized by comprising the following steps: the method for recycling petrochemical wastewater according to any one of claims 1 to 3, comprising the steps of:
(1) raw petrochemical wastewater enters a regulating reservoir device, and the water quality and the water quantity are regulated by utilizing a regulating reservoir;
(2) the effluent of the regulating reservoir enters an oil removal tank through a lift pump, compressed air and an oil removal agent are added, after full mixing reaction through a stirrer, oil substances are carried by micro bubbles to float upwards, and stay for 25min, and the oil substances are removed;
(3) the effluent of the oil removing tank enters a neutralization coagulation sedimentation tank, quicklime, NaOH, flocculating agents PAC and PAM are simultaneously added, the effluent enters a primary filter after sedimentation, and the filtered water enters an intermediate water tank after solid matters are filtered;
(4) the lift pump sends the filtered water of the middle water tank into a precision filter to remove residual nonionic impurities and partial ionic substances as pretreatment of 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 treated clear water meets the recycling requirement.
5. The method for recycling petrochemical wastewater according to claim 4, wherein quicklime and NaOH are added in the step (3) to adjust the pH of the wastewater to 8-9, the flocculant PAC is added in an amount of 5-20mg/L, and the PAM is added in an amount of 0.1-1 mg/L.
6. The method for recycling petrochemical wastewater according to claim 4, wherein in the step (3), quicklime and NaOH are added to adjust the pH value to 8.5-9, and flocculating agents PAC (polyaluminium chloride) 10-18mg/L and PAM (polyacrylamide) 0.4-0.8mg/L are added.
7. The method for recycling petrochemical wastewater according to any one of claims 4-5, wherein the resin of the membraneless electrodeionization device in the step (5) is regenerated electrically by using regenerated current densityIs 100 to 350A/m2Preferably, the regenerative current density is 200 to 350A/m2。
8. The method for recycling petrochemical wastewater according to claims 4-5, wherein the method comprises the following steps: the precision filter is filled with an ultrafiltration membrane or a nanofiltration membrane or the combination of the ultrafiltration membrane and the nanofiltration membrane.
9. The method for recycling petrochemical wastewater according to claims 4-5, wherein the method comprises the following steps: a pair of cathode and anode electrodes, both of which are platinized titanium electrodes, are arranged at two ends of a resin layer in the membraneless electrodeionization device.
10. The method for recycling petrochemical wastewater according to claim 9, wherein the method comprises the following steps: the preparation method of the platinum-plated 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 solution, 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 for preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111529001.1A CN114212914B (en) | 2021-12-14 | 2021-12-14 | Petrochemical wastewater recycling method and system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111529001.1A CN114212914B (en) | 2021-12-14 | 2021-12-14 | Petrochemical wastewater recycling method and system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114212914A true CN114212914A (en) | 2022-03-22 |
| CN114212914B CN114212914B (en) | 2023-05-05 |
Family
ID=80702030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111529001.1A Active CN114212914B (en) | 2021-12-14 | 2021-12-14 | Petrochemical wastewater recycling method and system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114212914B (en) |
Citations (15)
| 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 |
| JP2001170658A (en) * | 1999-12-17 | 2001-06-26 | Kurita Water Ind Ltd | Treating device for fluorine-containing waste water and treatment method |
| US20040188352A1 (en) * | 2003-03-28 | 2004-09-30 | Avijit Dey | 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 |
| JP2005329315A (en) * | 2004-05-19 | 2005-12-02 | Japan Organo Co Ltd | Method and apparatus for recovering water from drainage containing tetraalkyl ammonium ion |
| 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 |
| CN102815765A (en) * | 2012-08-30 | 2012-12-12 | 中国石油天然气股份有限公司 | Deep softening method of thick oil sewage |
| CN103505905A (en) * | 2012-06-18 | 2014-01-15 | 天津天士力现代中药资源有限公司 | Method for removing traditional Chinese medicine heavy metal by using chelate resin and ion exchange resin composition |
| JP2014151310A (en) * | 2013-02-13 | 2014-08-25 | Toshiba Corp | Water treatment method and water treatment equipment |
| 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 |
| 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 |
| CN114210374A (en) * | 2021-12-14 | 2022-03-22 | 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 (15)
| 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 |
| JP2001170658A (en) * | 1999-12-17 | 2001-06-26 | Kurita Water Ind Ltd | Treating device for fluorine-containing waste water and treatment method |
| US20040188352A1 (en) * | 2003-03-28 | 2004-09-30 | Avijit Dey | 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 |
| JP2005329315A (en) * | 2004-05-19 | 2005-12-02 | Japan Organo Co Ltd | Method and apparatus for recovering water from drainage containing tetraalkyl ammonium ion |
| 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 |
| CN103505905A (en) * | 2012-06-18 | 2014-01-15 | 天津天士力现代中药资源有限公司 | Method for removing traditional Chinese medicine heavy metal by using chelate resin and ion exchange resin composition |
| CN102815765A (en) * | 2012-08-30 | 2012-12-12 | 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 |
| 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 |
| 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 |
| CN114210374A (en) * | 2021-12-14 | 2022-03-22 | 宁波职业技术学院 | Ion exchange resin suitable for petrochemical wastewater treatment and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| SHEN,XL等: "Membrane-free-electrodeionization using graphene composite electrode to purify copper-containing wastewater" * |
| 万壮: "基于复合床的电去离子及其防垢技术的研究" * |
| 申小兰: "MFEDI处理低浓度含镶废水研究" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114212914B (en) | 2023-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10150685B2 (en) | Water reclamation method integrating magnetic resin adsorption and electrosorption | |
| CN108358362B (en) | Advanced treatment method of high-concentration organic wastewater | |
| CN103265133B (en) | Recycling method of papermaking advanced treatment wastewater based on chemical decalcification | |
| CN204727706U (en) | A kind of film electrical coupling system of Sewage advanced treatment | |
| CN106746131A (en) | A kind of organic wastewater reverse osmosis concentrated water oxidation and desalination process and system | |
| CN111423035B (en) | Combined treatment process system and method for circulating water of thermal power plant through chemical-free electrotechnology | |
| CN112939321A (en) | Steel wastewater zero-discharge treatment technology | |
| CN101694007B (en) | Treatment method of electroplating rinsewater | |
| CN104944646A (en) | Wastewater advanced treatment method coupling membrane and electricity | |
| CN109354134B (en) | Method for removing chroma of anodic oxidation dyeing wastewater through electric flocculation | |
| WO2020228638A1 (en) | Method for efficiently regenerating resin by using electrolytic salt solution | |
| CN101698523B (en) | Method for applying molded carbon in treatment of industrial waste water by electroflocculation | |
| CN113896346A (en) | Efficient treatment process for fluorine-containing wastewater | |
| CN107840495B (en) | Method for treating crude oil electric desalting wastewater | |
| CN214990901U (en) | Process system for treating precipitated white carbon black wastewater | |
| CN114212914B (en) | Petrochemical wastewater recycling method and system | |
| CN111807596A (en) | Process method for treating precipitated white carbon black wastewater | |
| CN111646604A (en) | Treatment method and device for refractory organic wastewater | |
| WO2023078105A1 (en) | Sewage treatment system and method | |
| CN212198606U (en) | One-way cation mixed exchange type water purification system and water purifier | |
| CN113371895A (en) | Process method and system for resourceful treatment of oil and gas field produced water | |
| CN210559900U (en) | Chemical nickel waste water electrocatalytic oxidation treatment system | |
| CN113105036A (en) | High-salinity water body desalting system based on electric adsorption technology | |
| CN111423032A (en) | Treatment method of CTP (computer to plate) flushing water in printing factory | |
| CN111423029A (en) | System and process for treating water in water tank, CTP (computer to plate) flushing water and glue to reach discharge standard |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |