Application of a liquid resin in treating copper-containing wastewater

Abstract

The present invention discloses an application of a liquid resin in treating copper-containing wastewater, and the copper-containing wastewater is copper-containing wastewater in the electronic industry; the liquid resin is composed of the following components in parts by mass: 1-2 parts of diethylenetriamine pentamethylenephosphonic acid, 0.5-2 parts of 2-hydroxy-5-nonylacetophenone oxime, 1-2 parts of salicylaldoxime, 0.1-0.2 parts of 2,6-di-tert-butylhydroquinone, and 10-20 parts of an organic solvent. The liquid resin of the present invention can form metal chelates with copper ions in a water environment with strong acidity (pH<1), strong complexing property and strong oxidizing property, so that the copper ions are efficiently captured and enriched in the liquid resin, and the service life of the liquid resin is effectively prolonged; when the liquid resin of the present invention is used to treat copper-containing wastewater in the electronic industry, by arranging three liquid resin towers connected end to end, and during operation, two of the three liquid resin towers are operated in series and one is regenerated, continuous production in the treatment process is realized.

Description

Technical Field

[0001] The present invention relates to the application of a liquid resin in treating copper-containing wastewater. Background Art

[0002] The copper-containing wastewater generated in the electronic industries such as semiconductors, panels, electroplating, etc. contains a large amount of copper ions, complex copper, hydrogen peroxide, hydrofluoric acid and other substances, and has the characteristics of strong acidity (pH < 1), strong oxidizing property, strong complexing property, etc. Compared with the treatment of ionic copper-containing wastewater in industries such as mines, smelters, chemical industries, and hardware, it has problems such as high treatment difficulty and high treatment cost. At present, the methods for treating this kind of complex water quality mainly include chemical coagulation and precipitation method. By adding a large amount of liquid caustic, heavy metal capturant, coagulant and flocculant and other chemicals, the copper in the wastewater is separated from the water in the form of chelate precipitate. The copper-containing sludge generated is hazardous waste sludge and needs to be outsourced for treatment at a high price. The effluent often has problems such as unqualified copper ion discharge due to water quality fluctuations.

[0003] Copper is a widely used metal, and treating it by precipitation is a waste of resources. The research of existing methods focuses on realizing the further resource utilization of copper after it is captured while treating copper-containing wastewater. For example, in Patent CN 103952551 A, 2-hydroxy-5-nonylbenzaldoxime, 2-hydroxy-5-nonylacetophenone oxime, 4-dodecyl-2-hydroxybenzaldehyde and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and kerosene are used as the main formulation to adsorb copper-containing wastewater, and the adsorption rate reaches 98%. However, it is only applicable to the adsorption of copper-containing wastewater with a pH of 2-8 and cannot treat strongly acidic wastewater with a pH < 1, which has limitations. Summary of the Invention

[0004] Object of the Invention: The object of the present invention is to provide an application of a liquid resin that can still have a high adsorption rate for copper ions in an aqueous environment with strong acidity (pH < 1), strong complexing property and strong oxidizing property in treating copper-containing wastewater.

[0005] Technical Solution: The liquid resin described in the present invention is composed of the following components in parts by mass: 1-2 parts of diethylenetriamine pentamethylenephosphonic acid, 0.5-2 parts of 2-hydroxy-5-nonylacetophenone oxime, 1-2 parts of salicylaldoxime, 0.1-0.2 parts of 2,6-di-tert-butyl-p-cresol, and 10-20 parts of organic solvent.

[0006] The preparation method of the above liquid resin includes the following steps:

[0007] (1) Stir and mix the formulated amount of diethylenetriamine pentamethylenephosphonic acid and 2-hydroxy-5-nonylacetophenone oxime at room temperature to obtain a mixture; 2-hydroxy-5-nonylacetophenone oxime has excellent phase separation property, which can improve the separation speed after the liquid resin adsorbs copper-containing wastewater;

[0008] (2) Add the formula amount of salicylaldoxime to the mixture in step (1), and after reacting at high temperature, product I with a network structure is obtained;

[0009] (3) Take the formula amount of 2,6 - di - tert - butyl - p - benzenediol (2,6 - di - tert - butyl - p - benzenediol is a solid and needs to be heated and dissolved), after heating and dissolving, add it to product I for dehydration reaction, and product II is obtained after the reaction;

[0010] (4) Mix product II with the formula amount of organic solvent to obtain a liquid resin. The liquid resin reacts with liquid copper - containing wastewater. Compared with solid resin and liquid copper - containing wastewater, the contact area between the liquid resin and copper wastewater is larger, and the copper - capturing efficiency is higher; in addition, product II is in a liquid viscous state with poor fluidity and poor separation effect, so it is dissolved in an organic solvent and then reacts with copper wastewater.

[0011] Under high - temperature conditions, the phosphorus - oxygen double bond of diethylenetriamine pentamethylenephosphonic acid rapidly reacts with the hydroxyl group in the hydroxy - imine structure C=N—OH of salicylaldoxime to form a hydrogen bond. Under the action of the hydrogen bond, multiple diethylenetriamine pentamethylenephosphonic acids are connected to multiple salicylaldoximes to form product I with a large molecular weight and a network three - dimensional structure. The lone pair electrons on the hydroxyl oxygen and oxime nitrogen of product I coordinate with copper ions in the wastewater. Product I with a large molecular weight and a network three - dimensional structure greatly enhances the adsorption and stability of copper ions (stability means that the adsorbed copper is not easily desorbed, and copper is stably adsorbed on the resin), so that it can stably capture copper ions under the condition of a higher hydrogen ion content (at pH < 1), and can also capture copper ions from complex copper;

[0012]

[0013] There is a hydroxy - imine structure C=N—OH (the hydroxy - imine structure is represented by RH) in salicylaldoxime, with a carbon - nitrogen double bond. The valence of the N atom is relatively low and it is prone to radical oxidation reaction. The oxidation reaction is as follows:

[0014]

[0015] RH + H2O2 → R - + HOO - + H2O

[0016] R - + H2O2 → ROO - + H2O

[0017] ROO - + RH → HOO - + 2R -

[0018] The hydroxy - imine structure is oxidized and decomposed into active free radicals (R- ), and this free radical can react with hydrogen peroxide to generate a new free radical (ROO - ). The cycle that repeats itself causes the oxidation reaction to proceed according to the free radical chain mechanism, leading to the oxidation of salicylaldoxime and the destruction of the three-dimensional network structure of product I, thereby reducing the adsorption and stability of copper ions. The alkyl groups on the benzene ring of 2,6-di-tert-butylhydroquinone disperse electrons and play a role in stabilizing free radicals. It can react with the chain-propagating free radicals (R - or ROO - ) in auto-oxidation, interrupting the chain reaction and playing an antioxidant role;

[0019]

[0020] By loading 2,6-di-tert-butylhydroquinone on product I, the chain reaction is reduced, the antioxidant property of the final product liquid resin is improved, the adsorption efficiency of the resin is guaranteed, the service life of the liquid resin is extended, and the high copper ion adsorption of product I is maintained;

[0021]

[0022] The three-dimensional network structure formed by diethylenetriamine pentamethylenephosphonic acid and salicylaldoxime has strong chelating ability for copper ions and can stably adsorb copper ions under the water quality condition of pH < 1. At the same time, it also has a high adsorption rate for complex copper. The alkyl groups on the benzene ring of 2,6-di-tert-butylhydroquinone disperse electrons, playing an effect of stabilizing free radicals, reducing the chain reaction, improving the antioxidant property of the final product liquid resin, guaranteeing the adsorption efficiency of the liquid resin, and extending the service life of the liquid resin.

[0023] Among them, in step (2), the reaction temperature is not lower than 60 °C; the role of high temperature is to reduce the reaction activation energy and promote the combination of the phosphorus-oxygen double bond and the hydroxyl group in the C=N—OH structure of the hydroxyimine.

[0024] Among them, in step (3), the heating temperature is 35 - 40 °C.

[0025] The regeneration method of the above liquid resin is specifically as follows: First, wash the liquid resin for treating copper-containing wastewater in the electronics industry. After washing, add nonylphenol and sulfuric acid with a mass fraction of not less than 15% to the liquid resin and treat for 5 - 8 min (each liquid resin tower is regenerated for 5 - 8 min) to obtain the regenerated liquid resin.

[0026] Among them, the addition amount of nonylphenol is 0.2 - 0.5 times the mass of the liquid resin; the added volume of sulfuric acid is 1 / 2 - 1 / 5 of the volume of the liquid resin.

[0027] Nonylphenol can form strong hydrogen bonds with hydroxyl groups and oxime groups under the action of concentrated sulfuric acid as a catalyst, weakening the chelating ability of hydroxyl groups and oxime groups with copper ions. Hydrogen ions displace copper ions, improving the regeneration efficiency of the liquid resin, and the regeneration rate of the liquid resin is as high as over 95%.

[0028]

[0029] The above-mentioned application of the liquid resin in treating copper-containing wastewater in the electronics industry.

[0030] Among them, the reactor adopted in the application process is as follows: It includes three liquid resin towers, and the three liquid resin towers are connected end to end; each liquid resin tower includes a waste liquid inlet, a waste liquid outlet, a regenerant inlet, and a regenerated liquid outlet; the waste liquid inlets of the three liquid resin towers are respectively connected to the waste liquid tank through liquid inlet pipes, and an electrically controlled valve I is provided on the liquid inlet pipes; the waste liquid outlets of the three liquid resin towers are connected to a liquid outlet pipe, and the liquid outlet pipe is divided into a first liquid outlet pipe and a second liquid outlet pipe. The upper-level liquid resin tower is connected to the waste liquid inlet of the lower-level liquid resin tower through the first liquid outlet pipe, and the second liquid outlet pipe of the liquid resin tower is connected to the subsequent water treatment unit; electrically controlled valves II and copper ion concentration detectors are provided on both the first liquid outlet pipe and the second liquid outlet pipe; the regenerated liquid outlets of the three liquid resin towers are connected to an external resource treatment unit through a drainage pipe, and an electrically controlled valve III is provided on the drainage pipe; the regenerant inlets of the three liquid resin towers are connected to the regenerant tank through a connecting pipe, and an electrically controlled valve IV is provided on the connecting pipe.

[0031] Among them, baffles for increasing the reaction time between the liquid resin and the copper-containing wastewater are provided inside the towers of the three liquid resin towers.

[0032] Among them, the specific operation process of the reactor is as follows: Two of the three liquid resin towers operate in series. When the two liquid resin towers operate in series for at least 18 hours, the electrically controlled valve on the liquid inlet pipe connecting the previous-level liquid resin tower and the waste liquid tank and the electrically controlled valve on the first liquid outlet pipe of the previous-level liquid resin tower are closed. At the same time, the electrically controlled valve on the connecting pipe connecting the current-level liquid resin tower and the regenerant tank and the electrically controlled valve on the drainage pipe of the current-level liquid resin tower are started; the electrically controlled valve on the liquid inlet pipe connecting the subsequent-level liquid resin tower and the waste liquid tank and the electrically controlled valve on the second liquid outlet pipe of the subsequent-level liquid resin tower are started, and the liquid outlet pipe of the subsequent-level liquid resin tower is switched to connect to the waste liquid inlet of the next-level liquid resin tower; the reactor is continuously operated in the above manner.

[0033] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The liquid resin of the present invention can generate metal chelates with copper ions in a strongly acidic (pH <1), strongly complexing and strongly oxidizing water environment, so that the copper ions are efficiently captured and enriched in the liquid resin, and the service life of the liquid resin is effectively extended; (2) After the liquid resin of the present invention is adsorbed and saturated, it is regenerated using nonylphenol and concentrated sulfuric acid. The regeneration method of the present invention makes the regeneration rate of the liquid resin as high as 95% or more. After regeneration, the liquid resin performs the next round of adsorption and capture of copper ions, effectively extending the service life of the liquid resin; (3) When the liquid resin of the present invention treats copper-containing wastewater in the electronics industry, three liquid resin towers connected end to end are set, and two of the three liquid resin towers are operated in series during the operation process to achieve continuous production. Since the liquid resin has a strong ability to capture copper ions and a good regeneration effect, the purity of (copper sulfate) in the regenerated liquid is high and can be utilized as a resource to form copper sulfate crystals through evaporation and crystallization, or to recover copper element through electrolysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 Flow chart of the reactor operation process. DETAILED DESCRIPTION

[0035] Example 1

[0036] The liquid resin of the present invention is composed of the following components in parts by mass: 1.5 parts of diethylenetriamine penta (methylene phosphonic acid), 1 part of 2-hydroxy-5-nonylacetophenone oxime, 1 part of salicylaldehyde oxime, 0.15 parts of 2,6-di-tert-butylhydroquinone and 15 parts of an organic solvent.

[0037] The method for preparing the liquid resin comprises the following steps:

[0038] (1) mixing a formulated amount of diethylenetriamine penta (methylene phosphonic acid) and 2-hydroxy-5-nonylacetophenone oxime at room temperature and stirring for 20 to 30 minutes to obtain a mixture;

[0039] (2) adding a formulated amount of salicylaldehyde oxime to the mixture of step (1), stirring at 60° C. for 20 to 30 minutes, to obtain a product I having a network structure;

[0040] (3) taking a formulated amount of 2,6-di-tert-butylhydroquinone, heating it to dissolve at 35-40° C., adding it to product I for dehydration reaction, and rapidly stirring for 5-10 minutes to obtain product II;

[0041] (4) Mix the product II with a formulated amount of an organic solvent and stir at room temperature for 30 minutes to obtain a liquid resin.

[0042] Comparative Example 1

[0043] A liquid resin is composed of the following components in parts by mass: 1.5 parts of diethylenetriamine pentamethylenephosphonic acid, 1 part of 2-hydroxy-5-nonylacetophenone oxime, 0.15 part of 2,6-di-tert-butyl-p-benzenediol, and 15 parts of organic solvent.

[0044] The preparation method of the above liquid resin includes the following steps:

[0045] (1) Mix and stir the formula amount of diethylenetriamine pentamethylenephosphonic acid and 2-hydroxy-5-nonylacetophenone oxime at room temperature for 20 - 30 min to obtain a mixture;

[0046] (2) Take the formula amount of 2,6-di-tert-butyl-p-benzenediol, heat and dissolve it at 35 - 40 °C, then add it to the mixture, and quickly stir for 5 - 10 min to obtain Product II;

[0047] (3) Mix Product II with the formula amount of organic solvent, and stir at room temperature for 30 min to obtain the liquid resin.

[0048] Comparative Example 2

[0049] A liquid resin is composed of the following components in parts by mass: 1.5 parts of diethylenetriamine pentamethylenephosphonic acid, 1 part of 2-hydroxy-5-nonylacetophenone oxime, 1 part of salicylaldoxime, and 15 parts of organic solvent.

[0050] The preparation method of the above liquid resin includes the following steps:

[0051] (1) Mix and stir the formula amount of diethylenetriamine pentamethylenephosphonic acid and 2-hydroxy-5-nonylacetophenone oxime at room temperature for 20 - 30 min to obtain a mixture;

[0052] (2) Add the formula amount of salicylaldoxime to the mixture in step (1), and stir at 60 °C for 20 - 30 min to obtain Product I in a network structure;

[0053] (3) Mix Product I with the formula amount of organic solvent, and stir at room temperature for 30 min to obtain the liquid resin.

[0054] Comparative Example 3

[0055] A liquid resin is composed of the following components in parts by mass: 1.5 parts of diethylenetriamine pentamethylenephosphonic acid, 1 part of salicylaldoxime, 0.15 part of 2,6-di-tert-butyl-p-benzenediol, and 15 parts of organic solvent.

[0056] The preparation method of the above liquid resin includes the following steps:

[0057] (1) Add the formula amount of salicylaldoxime to the formula amount of diethylenetriamine pentamethylenephosphonic acid, and stir at 60 °C for 20 - 30 min to obtain Product I in a network structure;

[0058] (2) Take the formulated amount of 2,6 - di - tert - butylhydroquinone, heat and dissolve it at 35 - 40 °C, then add it to Product I for dehydration reaction. After rapidly stirring for 5 - 10 min, Product II is obtained;

[0059] (3) Mix Product II with the formulated amount of organic solvent and stir at room temperature for 30 min to obtain a liquid resin.

[0060] Comparative Example 4

[0061] A liquid resin is composed of the following components in parts by mass: 0.5 part of diethylenetriamine pentamethylenephosphonic acid, 1 part of 2 - hydroxy - 5 - nonylacetophenone oxime, 2.5 parts of salicylaldoxime, 0.15 part of 2,6 - di - tert - butylhydroquinone, and 15 parts of organic solvent.

[0062] The preparation method of the above - mentioned liquid resin includes the following steps:

[0063] (1) Mix the formulated amount of diethylenetriamine pentamethylenephosphonic acid and 2 - hydroxy - 5 - nonylacetophenone oxime at room temperature and stir for 20 - 30 min to obtain a mixture;

[0064] (2) Add the formulated amount of salicylaldoxime to the mixture in step (1), and stir at 60 °C for 20 - 30 min to obtain Product I;

[0065] (3) Take the formulated amount of 2,6 - di - tert - butylhydroquinone, heat and dissolve it at 35 - 40 °C, then add it to Product I for dehydration reaction. After rapidly stirring for 5 - 10 min, Product II is obtained;

[0066] (4) Mix Product II with the formulated amount of organic solvent and stir at room temperature for 30 min to obtain a liquid resin.

[0067] Comparative Example 5

[0068] A liquid resin is composed of the following components in parts by mass: 1.5 parts of 2 - ethylhexylphosphinic acid, 1 part of 2 - hydroxy - 5 - nonylacetophenone oxime, 1 part of salicylaldoxime, 0.15 part of 2,6 - di - tert - butylhydroquinone, and 15 parts of organic solvent.

[0069] The preparation method of the above - mentioned liquid resin includes the following steps:

[0070] (1) Mix the formulated amount of 2 - ethylhexylphosphinic acid and 2 - hydroxy - 5 - nonylacetophenone oxime at room temperature and stir for 20 - 30 min to obtain a mixture;

[0071] (2) Add the formulated amount of salicylaldoxime to the mixture in step (1), and stir at 60 °C for 20 - 30 min to obtain Product I;

[0072] (3) Weigh out the formulated amount of 2,6 - di - tert - butyl - p - benzoquinone, heat and dissolve it at 35 - 40 °C, then add it to Product I for dehydration reaction. After rapidly stirring for 5 - 10 min, Product II is obtained;

[0073] (4) Mix Product II with the formulated amount of organic solvent and stir at room temperature for 30 min to obtain a liquid resin.

[0074] Example 2

[0075] Treat the liquid resin obtained in Example 1 with copper etching waste liquid (in the copper etching waste liquid, the water volume is 60 m 3 / d, the copper ion concentration is 4500 mg / L, the complexed copper concentration is 2000 mg / L, the hydrogen peroxide concentration is 180000 mg / L, the COD content is 60000 mg / L, the fluoride ion concentration is 1000 mg / L, the total phosphorus is 500 mg / L, pH < 0.85). The specific steps are as follows:

[0076] (1) Collect the high - concentration copper - containing wastewater through pipelines and feed it into the homogenization tank, with a residence time of 4 h;

[0077] (2) Feed the effluent from the homogenization tank into the reactor. The reactor includes three liquid resin towers, namely Liquid Resin Tower A, Liquid Resin Tower B, and Liquid Resin Tower C (the filling amount of the liquid resin in Liquid Resin Tower A, Liquid Resin Tower B, and Liquid Resin Tower C is 20 m 3), baffles are provided in the tower bodies of the three liquid resin towers to increase the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater first enters the liquid resin tower A and the liquid resin tower B connected in series for adsorption, the liquid resin tower A takes in water, and the liquid resin tower B takes out water, when the liquid resin in the liquid resin tower A is completely adsorbed and saturated (after 18 hours of operation), the copper ion concentration in the water outlet of the liquid resin tower B is detected to be 20-30 mg / L, and the liquid resin tower A enters the regeneration process, and the liquid resin tower B and the liquid resin tower C are connected in series to start the adsorption operation, the liquid resin tower B takes in water, and the liquid resin tower C takes out water; when the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the copper ion concentration in the water outlet of the liquid resin tower C is detected to be 20-30 mg / L, and the liquid resin tower B enters the regeneration process, and the liquid resin Tower C and liquid resin tower A are connected in series in sequence to start adsorption operation, liquid resin tower C takes in water, and liquid resin tower A discharges water; when the liquid resin in liquid resin tower C is completely adsorbed and saturated (after running for 18 hours), it is detected that the copper ion concentration in the waste liquid effluent of liquid resin tower A is 20-30 mg / L, liquid resin tower C enters the regeneration process, liquid resin tower A and liquid resin tower B are connected in series in sequence to start adsorption operation, and the above method is repeated to continuously operate the reactor; after A+B, B+C, and C+A resin towers are each operated for 18 hours, the copper concentration of the system effluent can reach 20-30 mg / L; the saturated adsorption capacity of the liquid resin is more than 99%; the regenerated liquid obtained by liquid resin tower A, liquid resin tower B and liquid resin tower C is discharged into the subsequent electrolysis system to generate high-purity copper elemental substance, the copper purity is 99.99%, and the copper recovery rate reaches 99.97%.

[0078] Before the liquid resin tower regeneration process, the liquid resin is first cleaned with pure water to wash off a large amount of COD attached to the liquid resin. The pure water cleaning flow rate is 15BV / h, and the pure water volume is 1BV. Then, nonylphenol (the amount of nonylphenol added is 0.3 times the mass of the liquid resin) and 20% sulfuric acid (the added volume of sulfuric acid is 1 / 3 of the volume of the liquid resin) are used to regenerate the liquid resin. The regeneration time is 7.5 minutes, the regeneration rate of the liquid resin is 96%, the regeneration agent flow rate is 8BV / h, and the dosage is 1BV.

[0079] Example 3

[0080] The liquid resin obtained in Example 1 was added to the copper etching waste liquid (the water volume in the copper etching waste liquid was 60m 3 / d, copper ion concentration of 4500mg / L, complex copper concentration of 2000mg / L, hydrogen peroxide concentration of 180000mg / L, COD content of 60000mg / L, fluoride ion concentration of 1000mg / L, total phosphorus of 500mg / L, pH<0.85), specifically:

[0081] (1) The high-concentration copper-containing wastewater is collected through a pipeline and then enters a homogenization tank for a residence time of 4 hours;

[0082] (2) The effluent from the homogenization tank enters the reactor, which includes three liquid resin towers, namely liquid resin tower A, liquid resin tower B and liquid resin tower C (the filling amount of liquid resin in liquid resin tower A, liquid resin tower B and liquid resin tower C is 20m 3 ), baffles are provided in the tower bodies of the three liquid resin towers to increase the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater first enters the liquid resin tower A and the liquid resin tower B connected in series for adsorption, the liquid resin tower A takes in water, and the liquid resin tower B takes out water, when the liquid resin in the liquid resin tower A is completely adsorbed and saturated (after 18 hours of operation), the copper ion concentration in the water outlet of the liquid resin tower B is detected to be 20-30 mg / L, and the liquid resin tower A enters the regeneration process, and the liquid resin tower B and the liquid resin tower C are connected in series to start the adsorption operation, the liquid resin tower B takes in water, and the liquid resin tower C takes out water; when the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the copper ion concentration in the water outlet of the liquid resin tower C is detected to be 20-30 mg / L, and the liquid resin tower B enters the regeneration process, and the liquid resin Tower C and liquid resin tower A are connected in series in sequence to start adsorption operation, liquid resin tower C takes in water, and liquid resin tower A discharges water; when the liquid resin in liquid resin tower C is completely adsorbed and saturated (after running for 18 hours), it is detected that the copper ion concentration in the waste liquid effluent of liquid resin tower A is 20-30 mg / L, liquid resin tower C enters the regeneration process, liquid resin tower A and liquid resin tower B are connected in series in sequence to start adsorption operation, and the above method is repeated to continuously operate the reactor; after A+B, B+C, and C+A resin towers are each operated for 18 hours, the copper concentration of the system effluent can reach 20-30 mg / L; the saturated adsorption capacity of the liquid resin is more than 99%; the regenerated liquid obtained by liquid resin tower A, liquid resin tower B and liquid resin tower C is discharged into the subsequent electrolysis system to generate high-purity copper elemental substance, the copper purity is 99.99%, and the copper recovery rate reaches 99.97%.

[0083] Before the liquid resin tower regeneration process, the liquid resin is first cleaned with pure water to wash off the large amount of COD attached to the liquid resin. The pure water cleaning flow rate is 15BV / h, and the pure water volume is 1BV. Then, sulfuric acid with a mass fraction of 20% (the added volume of sulfuric acid is 1 / 3 of the volume of the liquid resin) is used to regenerate the liquid resin. The regeneration time is 7.5min, and the regeneration rate of the liquid resin is 87%. The remaining 12-13% of copper still remains in the liquid resin; the regeneration agent flow rate is 8BV / h, and the dosage is 1BV. The reason for the reduced regeneration efficiency is that nonylphenol is not introduced into the regeneration agent, which reduces the regeneration efficiency.

[0084] Example 4

[0085] The liquid resin obtained in Comparative Example 1 was added to the copper etching waste liquid (the water volume in the copper etching waste liquid was 60m 3 / d, copper ion concentration of 4500mg / L, complex copper concentration of 2000mg / L, hydrogen peroxide concentration of 180000mg / L, COD content of 60000mg / L, fluoride ion concentration of 1000mg / L, total phosphorus of 500mg / L, pH<0.85), specifically:

[0086] (1) The high-concentration copper-containing wastewater is collected through a pipeline and then enters a homogenization tank for a residence time of 4 hours;

[0087] (2) The effluent from the homogenization tank enters the reactor, which includes three liquid resin towers, namely liquid resin tower A, liquid resin tower B and liquid resin tower C (the filling amount of liquid resin in liquid resin tower A, liquid resin tower B and liquid resin tower C is 20m 3 ), baffles are provided in the tower bodies of the three liquid resin towers to increase the reaction time of the liquid resin and the copper-containing wastewater; the copper-containing wastewater first enters the liquid resin tower A and the liquid resin tower B connected in series for adsorption, the liquid resin tower A takes in water, and the liquid resin tower B discharges water, when the liquid resin in the liquid resin tower A is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower A enters the regeneration process, the liquid resin tower B and the liquid resin tower C are connected in series to start the adsorption operation, the liquid resin tower B takes in water, and the liquid resin tower C discharges water; when the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower B enters the regeneration process, and the liquid resin tower C and the liquid resin tower A are connected in series to start the adsorption operation, the liquid resin tower B takes in water, and the liquid resin tower C discharges water; when the liquid resin in the liquid resin tower B is completely adsorbed and saturated (after 18 hours of operation), the liquid resin tower B enters the regeneration process, and the liquid resin tower C and the liquid resin tower A are connected in series The adsorption operation starts in series for the second time, the liquid resin tower C takes in water, and the liquid resin tower A discharges water; when the liquid resin in the liquid resin tower C is completely adsorbed and saturated (after running for 18 hours), the liquid resin tower C enters the regeneration process, and the liquid resin tower A and the liquid resin tower B are connected in series in sequence to start the adsorption operation, and the reactor is continuously operated by repeating the above method; after the A+B, B+C, and C+A resin towers are each operated for 18 hours, the copper concentration of the system outlet water is 1260 mg / L, of which the complex copper is 600 mg / L; the regenerated liquid obtained from the liquid resin tower A, the liquid resin tower B, and the liquid resin tower C is discharged into the subsequent electrolysis system to generate high-purity copper element, the copper purity is 99.95%, and the copper recovery rate reaches 99.2%.

[0088] Before the liquid resin tower regeneration process, the liquid resin is first cleaned with pure water to wash off a large amount of COD attached to the liquid resin. The pure water cleaning flow rate is 15BV / h, and the pure water volume is 1BV. Then, nonylphenol (the amount of nonylphenol added is 0.3 times the mass of the liquid resin) and 20% sulfuric acid (the added volume of sulfuric acid is 1 / 3 of the volume of the liquid resin) are used to regenerate the liquid resin. The regeneration time is 7.5 minutes, the regeneration rate of the liquid resin is 95%, the regeneration agent flow rate is 8BV / h, and the dosage is 1BV.

[0089] Example 5

[0090] The liquid resin obtained in Comparative Example 2 was used to treat the copper etching waste liquid (in the copper etching waste liquid, the water volume was 60 m 3 / d, the copper ion concentration was 4500 mg / L, the complexed copper concentration was 2000 mg / L, the hydrogen peroxide concentration was 180000 mg / L, the COD content was 60000 mg / L, the fluoride ion concentration was 1000 mg / L, the total phosphorus was 500 mg / L, and the pH < 0.85). The specific treatment steps were as follows:

[0091] (1) The high-concentration copper-containing wastewater was collected through pipelines and then entered the homogenization tank, with a residence time of 4 h;

[0092] (2) The effluent from the homogenization tank entered the reactor. The reactor included three liquid resin towers, namely Liquid Resin Tower A, Liquid Resin Tower B, and Liquid Resin Tower C (the filling amount of the liquid resin in Liquid Resin Tower A, Liquid Resin Tower B, and Liquid Resin Tower C was 20 m 3 ). Baffles were installed in the towers of the three liquid resin towers to increase the reaction time between the liquid resin and the copper-containing wastewater. The copper-containing wastewater first entered Liquid Resin Tower A and Liquid Resin Tower B connected in series for adsorption. Liquid Resin Tower A was the inlet and Liquid Resin Tower B was the outlet. When the liquid resin in Liquid Resin Tower A was completely saturated by adsorption (after running for 18 hours), Liquid Resin Tower A entered the regeneration process at this time, and Liquid Resin Tower B and Liquid Resin Tower C were connected in series to start the adsorption operation. Liquid Resin Tower B was the inlet and Liquid Resin Tower C was the outlet. When the liquid resin in Liquid Resin Tower B was completely saturated by adsorption (after running for 18 hours), Liquid Resin Tower B entered the regeneration process at this time, and Liquid Resin Tower C and Liquid Resin Tower A were connected in series to start the adsorption operation. Liquid Resin Tower C was the inlet and Liquid Resin Tower A was the outlet. When the liquid resin in Liquid Resin Tower C was completely saturated by adsorption (after running for 18 hours), Liquid Resin Tower C entered the regeneration process at this time, and Liquid Resin Tower A and Liquid Resin Tower B were connected in series to start the adsorption operation. The reactor was continuously operated in the above manner;

[0093] Table 1 shows the copper adsorption efficiency of the liquid resin in Comparative Example 2 after running for 1 - 6 cycles (each cycle was 18 hours) and the copper ion concentration in the system effluent

[0094]

[0095] As can be seen from Table 1, as the number of operating cycles increased, the adsorption efficiency of the liquid resin gradually decreased, and the copper concentration in the system effluent became higher and higher. The reason was that 2,6-di-tert-butylhydroquinone antioxidant was not introduced into the liquid resin, resulting in the oxidation of the liquid resin by hydrogen peroxide and the gradual decrease of the adsorption efficiency.

[0096] Before the regeneration process of the liquid resin tower, the liquid resin is first washed with pure water to wash down a large amount of COD adhered to the liquid resin. The flow rate of pure water for washing is 15 BV / h, and the amount of pure water is 1 BV. Then, nonylphenol (the addition amount of nonylphenol is 0.3 times the mass of the liquid resin) and sulfuric acid with a mass fraction of 20% (the added volume of sulfuric acid is 1 / 3 of the volume of the liquid resin) are used for the regeneration of the liquid resin. The regeneration time is 7.5 min, the regeneration rate of the liquid resin is 95.8%, the flow rate of the regenerant is 8 BV / h, and the dosage of the reagent is 1 BV.

[0097] Example 6

[0098] The liquid resin obtained in Comparative Example 3 is used to treat the copper etching waste liquid (in the copper etching waste liquid, the water volume is 60 m 3 / d, the copper ion concentration is 4500 mg / L, the complexed copper concentration is 2000 mg / L, the hydrogen peroxide concentration is 180000 mg / L, the COD content is 60000 mg / L, the fluoride ion concentration is 1000 mg / L, the total phosphorus is 500 mg / L, and the pH < 0.85). Specifically:

[0099] (1) The high-concentration copper-containing wastewater is collected through a pipeline and enters the homogenization tank, with a residence time of 4 h;

[0100] (2) The effluent from the homogenization tank enters the reactor. The reactor includes three liquid resin towers, namely liquid resin tower A, liquid resin tower B, and liquid resin tower C (the filling amount of the liquid resin in liquid resin tower A, liquid resin tower B, and liquid resin tower C is 20 m 3) There are baffle plates in the towers of the three liquid resin towers to increase the reaction time between the liquid resin and the copper-containing wastewater. The copper-containing wastewater first enters the serially connected Liquid Resin Tower A and Liquid Resin Tower B for adsorption. Liquid Resin Tower A takes in water and Liquid Resin Tower B discharges water. When the liquid resin in Liquid Resin Tower A is completely saturated with adsorption (after running for 18 hours), Liquid Resin Tower A then enters the regeneration process. Liquid Resin Tower B and Liquid Resin Tower C are connected in series to start the adsorption operation. Liquid Resin Tower B takes in water and Liquid Resin Tower C discharges water. When the liquid resin in Liquid Resin Tower B is completely saturated with adsorption (after running for 18 hours), Liquid Resin Tower B then enters the regeneration process. Liquid Resin Tower C and Liquid Resin Tower A are connected in series in turn to start the adsorption operation. Liquid Resin Tower C takes in water and Liquid Resin Tower A discharges water. When the liquid resin in Liquid Resin Tower C is completely saturated with adsorption (after running for 18 hours), Liquid Resin Tower C then enters the regeneration process. Liquid Resin Tower A and Liquid Resin Tower B are connected in series in turn to start the adsorption operation. The reactor runs continuously in the above way. After A+B, B+C, and C+A resin towers each run for 18 hours, the copper concentration in the system effluent is 2500 mg / L. The reason is that there is a lack of 2-hydroxy-5-nonylacetophenone oxime in the liquid resin, which leads to a slow separation rate after the reaction between the liquid resin and the copper-containing wastewater. As a result, part of the liquid resin will be discharged together with the effluent, causing the amount of liquid resin in the resin tower to gradually decrease and the copper adsorption rate of the copper-containing wastewater to gradually decrease, resulting in a gradual increase in the copper concentration of the system effluent.

[0101] Before the regeneration process of the liquid resin tower, the liquid resin is first washed with pure water to wash down a large amount of COD adhered to the liquid resin. The flow rate of the pure water for washing is 15 BV / h, and the amount of pure water is 1 BV. Then, nonylphenol (the addition amount of nonylphenol is 0.3 times the mass of the liquid resin) and sulfuric acid with a mass fraction of 20% (the added volume of sulfuric acid is 1 / 3 of the volume of the liquid resin) are used for the regeneration of the liquid resin. The regeneration time is 7.5 minutes, the regeneration rate of the liquid resin is 96%, the flow rate of the regenerant is 8 BV / h, and the dosage of the reagent is 1 BV.

[0102] Example 7

[0103] The liquid resin obtained in Comparative Example 4 is used to treat the copper etching waste liquid (in the copper etching waste liquid, the water volume is 60 m 3 / d, the copper ion concentration is 4500 mg / L, the complexed copper concentration is 2000 mg / L, the hydrogen peroxide concentration is 180000 mg / L, the COD content is 60000 mg / L, the fluoride ion concentration is 1000 mg / L, the total phosphorus is 500 mg / L, and the pH < 0.85). Specifically:

[0104] (1) The high-concentration copper-containing wastewater is collected through pipelines and enters the homogenization tank, with a residence time of 4 hours;

[0105] (2) Feed the effluent from the equalization tank into the reactor. The reactor includes three liquid resin towers, namely liquid resin tower A, liquid resin tower B, and liquid resin tower C (the filling amount of liquid resin in liquid resin tower A, liquid resin tower B, and liquid resin tower C is 20 m 3 ), and baffles are provided in the towers of the three liquid resin towers to increase the reaction time between the liquid resin and the copper-containing wastewater. The copper-containing wastewater first enters liquid resin tower A and liquid resin tower B connected in series in sequence for adsorption. Liquid resin tower A is the inlet and liquid resin tower B is the outlet. When the liquid resin in liquid resin tower A is completely saturated by adsorption (after running for 18 hours), at this time, liquid resin tower A enters the regeneration process, and liquid resin tower B and liquid resin tower C are connected in series to start the adsorption operation. Liquid resin tower B is the inlet and liquid resin tower C is the outlet. When the liquid resin in liquid resin tower B is completely saturated by adsorption (after running for 18 hours), at this time, liquid resin tower B enters the regeneration process, and liquid resin tower C and liquid resin tower A are connected in series in sequence to start the adsorption operation. Liquid resin tower C is the inlet and liquid resin tower A is the outlet. When the liquid resin in liquid resin tower C is completely saturated by adsorption (after running for 18 hours), at this time, liquid resin tower C enters the regeneration process, and liquid resin tower A and liquid resin tower B are connected in series in sequence to start the adsorption operation. Repeat the above method to continuously operate the reactor. After A+B, B+C, and C+A resin towers each run for 18 h, the copper concentration in the effluent of the system is 855 mg / L, among which the complexed copper is 720 mg / L. It can be seen that the saturated adsorption capacity of the liquid resin is relatively low, and the content of complexed copper in the effluent is relatively high, which is caused by the reduction of the adsorption capacity and stability of the liquid resin. This liquid resin changes the mass ratio of diethylenetriamine pentamethylenephosphonic acid, 2-hydroxy-5-nonylacetophenone oxime, and salicylaldoxime, that is, the content of diethylenetriamine pentamethylenephosphonic acid in the liquid resin accounts for a relatively small proportion, and the content of salicylaldoxime accounts for a relatively high proportion, forming a relatively small number of network structures (relatively low molecular weight). More is that salicylaldoxime alone forms a single-chain chelate with copper, resulting in the reduction of the overall adsorption capacity and stability of the liquid resin.

[0106] Before the regeneration process of the liquid resin tower, first wash the liquid resin with pure water to wash down a large amount of COD adhered to the liquid resin. The washing flow rate of pure water is 15 BV / h, and the amount of pure water is 1 BV. Then use nonylphenol (the addition amount of nonylphenol is 0.3 times the mass of the liquid resin) and sulfuric acid with a mass fraction of 20% (the added volume of sulfuric acid is 1 / 3 of the volume of the liquid resin) to regenerate the liquid resin. The regeneration time is 7.5 min, the regeneration rate of the liquid resin is 96%, the regeneration agent flow rate is 8 BV / h, and the dosage of the agent is 1 BV.

[0107] Example 8

[0108] Use the liquid resin obtained in Comparative Example 5 for the copper etching waste liquid (in the copper etching waste liquid, the water volume is 60 m 3 / d, with a copper ion concentration of 4500 mg / L, a complexed copper concentration of 2000 mg / L, a hydrogen peroxide concentration of 180000 mg / L, a COD content of 60000 mg / L, a fluoride ion concentration of 1000 mg / L, and a total phosphorus of 500 mg / L, pH < 0.85) for treatment, specifically as follows:

[0109] (1) The high-concentration copper-containing wastewater is collected through pipelines and enters the homogenization tank, with a residence time of 4 h;

[0110] (2) The effluent from the homogenization tank enters the reactor. The reactor includes three liquid resin towers, namely liquid resin tower A, liquid resin tower B, and liquid resin tower C (the filling amount of the liquid resin in liquid resin tower A, liquid resin tower B, and liquid resin tower C is 20 m 3 ), and baffle plates are provided in the towers of the three liquid resin towers to increase the reaction time between the liquid resin and the copper-containing wastewater; the copper-containing wastewater first enters the sequentially connected liquid resin tower A and liquid resin tower B for adsorption. Liquid resin tower A takes in water and liquid resin tower B discharges water. When the liquid resin in liquid resin tower A is completely adsorbed and saturated (after running for 18 hours), at this time, liquid resin tower A enters the regeneration process, and liquid resin tower B and liquid resin tower C are connected in series to start the adsorption operation. Liquid resin tower B takes in water and liquid resin tower C discharges water; when the liquid resin in liquid resin tower B is completely adsorbed and saturated (after running for 18 hours), at this time, liquid resin tower B enters the regeneration process, and liquid resin tower C and liquid resin tower A are sequentially connected in series to start the adsorption operation. Liquid resin tower C takes in water and liquid resin tower A discharges water; when the liquid resin in liquid resin tower C is completely adsorbed and saturated (after running for 18 hours), at this time, liquid resin tower C enters the regeneration process, and liquid resin tower A and liquid resin tower B are sequentially connected in series to start the adsorption operation. Repeat the above method to continuously operate the reactor; after A + B, B + C, and C + A resin towers each run for 18 h, the copper concentration in the system effluent is 2025 mg / L, of which the complexed copper is 760 mg / L; the reason is that 2-ethylhexyl phosphinic acid has only one phosphorus-oxygen double bond, which forms a hydrogen bond with the hydroxyl group in the hydroxyimine structure C=N-OH of salicylaldoxime, and the formed product is a single-chain structure. Therefore, the adsorption capacity and stability of the liquid resin for copper are both reduced;

[0111]

[0112] Before the regeneration process of the liquid resin tower, the liquid resin is first washed with pure water to wash down a large amount of COD adhered to the liquid resin. The flow rate of the pure water for washing is 15 BV / h, and the amount of pure water is 1 BV. Then, nonylphenol (the addition amount of nonylphenol is 0.3 times the mass of the liquid resin) and sulfuric acid with a mass fraction of 20% (the added volume of sulfuric acid is 1 / 3 of the volume of the liquid resin) are used for the regeneration of the liquid resin. The regeneration time is 7.5 min, the regeneration rate of the liquid resin is 96%, the flow rate of the regenerant is 8 BV / h, and the dosage of the reagent is 1 BV.

Claims

1. Application of a liquid resin in treating copper-containing wastewater, characterized in that: The copper-containing wastewater is copper-containing wastewater from the electronics industry; the liquid resin is composed of the following components in parts by mass: 1-2 parts of diethylenetriamine pentamethylenephosphonic acid, 0.5-2 parts of 2-hydroxy-5-nonylacetophenone oxime, 1-2 parts of salicylaldoxime, 0.1-0.2 parts of 2,6-di-tert-butyl-p-benzenediol, and 10-20 parts of organic solvent; The preparation method of the above liquid resin includes the following steps: (1) Stir and mix the formula amount of diethylenetriamine pentamethylenephosphonic acid and 2-hydroxy-5-nonylacetophenone oxime at room temperature to obtain a mixture; (2) Add the formula amount of salicylaldoxime to the mixture in step (1), and after reacting at high temperature, obtain product I with a network structure; (3) Take the formula amount of 2,6-di-tert-butyl-p-benzenediol, heat and dissolve it, and then put it into product I for dehydration reaction, and obtain product II after the reaction; (4) Mix product II with the formula amount of organic solvent to obtain a liquid resin.

2. The application of the liquid resin according to claim 1 in treating copper-containing wastewater, characterized in that, The reactor used in the application process is: including three liquid resin towers, which are connected end to end; each liquid resin tower includes a waste liquid inlet, a waste liquid outlet, a regenerant inlet, and a regenerated liquid outlet; the waste liquid inlets of the three liquid resin towers are respectively connected to the waste liquid tank through the liquid inlet pipeline, and an electric control valve I is provided on the liquid inlet pipeline; the waste liquid outlets of the three liquid resin towers are connected to the liquid outlet pipeline, and the liquid outlet pipeline is divided into a first liquid outlet pipeline and a second liquid outlet pipeline. The upper-level liquid resin tower is connected to the waste liquid inlet of the lower-level liquid resin tower through the first liquid outlet pipeline, and the second liquid outlet pipeline of the liquid resin tower is connected to the subsequent water treatment unit; electric control valves II and copper ion concentration detectors are provided on both the first liquid outlet pipeline and the second liquid outlet pipeline; the regenerated liquid outlets of the three liquid resin towers are connected to the external resource treatment unit through the drain pipeline, and an electric control valve III is provided on the drain pipeline; the regenerant inlets of the three liquid resin towers are connected to the regenerant tank through the connection pipeline, and an electric control valve IV is provided on the connection pipeline.

3. The application of the liquid resin according to claim 2 in treating copper-containing wastewater, characterized in that: Baffles for increasing the reaction time between the liquid resin and the copper-containing wastewater are provided in the tower bodies of the three liquid resin towers.

4. The application of the liquid resin according to claim 2 in treating copper-containing wastewater, characterized in that, The specific operation process of the reactor is as follows: Two of the three liquid resin towers operate in series. When the two liquid resin towers operate in series for at least 18 hours, close the electric control valve on the liquid inlet pipeline between the previous-level liquid resin tower and the waste liquid tank and the electric control valve on the first liquid outlet pipeline of the previous-level liquid resin tower. At the same time, start the electric control valve on the connection pipeline between this level of liquid resin tower and the regenerant tank and the electric control valve on the drain pipeline of this level of liquid resin tower; start the electric control valve on the liquid inlet pipeline between the subsequent-level liquid resin tower and the waste liquid tank and the electric control valve on the second liquid outlet pipeline of the subsequent-level liquid resin tower, and switch the liquid outlet pipeline of the subsequent-level liquid resin tower to connect to the waste liquid inlet of the next-level liquid resin tower; repeat the above method to continuously operate the reactor.

Images