CN114084984A - Method for recovering palladium from biphenyl tetracarboxylic acid palladium-containing wastewater - Google Patents
Method for recovering palladium from biphenyl tetracarboxylic acid palladium-containing wastewater Download PDFInfo
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Abstract
The invention belongs to the technical field of wastewater treatment, and provides a method for recovering palladium from biphenyl tetracarboxylic acid palladium-containing wastewater. The method provided by the invention comprises the steps of pretreating the palladium-containing wastewater of the biphenyltetracarboxylic acid to obtain palladium ion-containing wastewater; the palladium ion-containing wastewater enters a three-stage electrolytic cyclone for extraction, and the palladium is recovered by washing the cathode of the three-stage electrolytic cyclone with water; the anode of the three-stage electrolytic cyclone comprises a titanium substrate and a platinum layer wrapped on the surface of the titanium substrate. According to the invention, the three-stage electrolytic cyclone is utilized to recover metal palladium, the anode active substance of the three-stage electrolytic cyclone is set to be metal platinum with the potential similar to that of palladium metal, so that reduction of palladium ions is facilitated, palladium is attached to a cathode in the form of a palladium simple substance, and recovery is simple; and flocculation precipitation cannot be caused in the electrolysis process, and no sludge solid waste is generated. The data of the embodiment show that the recovery rate of palladium in the palladium-containing wastewater of the biphenyltetracarboxylic acid by the method is 98.9-99.01%.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for recovering palladium from biphenyl tetracarboxylic acid palladium-containing wastewater.
Background
3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride is an important monomer of polyimide, can be polymerized with various amines to generate polyimide, is an indispensable material for wearable equipment, folding screen mobile phones, folding screen computers and the like, and has an obviously increased demand in recent years along with the rapid development of hot science and technology 5G, folding screen mobile phones, wearable equipment, folding screen mobile phones, folding screen computers and the like.
The 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride is 4-chlorophthalic tetracarboxylic acid, which is subjected to catalytic coupling, acidification and refining to obtain 3,3 ', 4, 4' -biphenyl tetracarboxylic acid, and the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid is subjected to dehydration to obtain 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride. In the process of producing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, wastewater with palladium content of about 7 ppm is generated in the catalytic coupling process, and if the wastewater is not properly treated and is randomly discharged, the ecological environment is seriously damaged.
The existing methods for treating the palladium-containing wastewater comprise a coagulating sedimentation method and a resin absorption method. Wherein, the resin absorption method needs to be combined with incineration, and the generated smoke can cause secondary pollution; and the recovery efficiency of palladium is low; the resin absorption method is less in application, and the treatment of the palladium-containing wastewater is mainly performed by a coagulating sedimentation method. Mixing the palladium-containing wastewater with a coagulant by a coagulating sedimentation method, and precipitating; however, the method leads palladium to enter the sludge along with the precipitation, so that the palladium cannot be effectively recovered; moreover, the large amount of sludge produced presents a serious sludge disposal problem.
Therefore, a method for effectively recovering the metal palladium in the palladium-containing wastewater is urgently needed.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for recovering palladium from a biphenyltetracarboxylic acid palladium-containing wastewater. The method provided by the invention can recover palladium from the biphenyl tetracarboxylic acid palladium-containing wastewater, and no solid waste is generated.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for recovering palladium from biphenyl tetracarboxylic acid palladium-containing wastewater, which comprises the following steps:
pretreating the biphenyl tetracarboxylic acid palladium-containing wastewater to obtain palladium ion-containing wastewater;
enabling the palladium ion-containing wastewater to enter a three-stage electrolytic cyclone for electrolytic deposition, and pickling the cathode of the three-stage electrolytic cyclone to obtain palladium;
the anode of the three-stage electrolytic cyclone comprises a titanium substrate and a platinum layer wrapped on the surface of the titanium substrate.
Preferably, the thickness of the platinum layer is 20-100 μm.
Preferably, the cathode of the three-stage electrolytic cyclone is made of zinc, iron or aluminum.
Preferably, in the electrolytic deposition process, the voltage of the three-stage electrolytic cyclone is direct current voltage; the direct current voltage is 12-25V.
Preferably, the dc voltage is a rectangular wave voltage.
Preferably, the voltage pulse frequency of the rectangular wave voltage is 20-35 kHz.
Preferably, the pre-treatment comprises the steps of:
removing organic matters from the biphenyl tetracarboxylic acid palladium-containing wastewater to obtain a mixed solution containing palladium and palladium ions;
ionizing the mixed solution containing palladium and palladium ions to obtain the palladium ion-containing wastewater.
Preferably, the step of removing the organic matter comprises: concentrating the biphenyl tetracarboxylic acid palladium-containing wastewater, adjusting the obtained concentrated wastewater to be acidic, and filtering to obtain the mixed solution containing palladium and palladium ions; the pH value of the acidity is 1-1.5.
Preferably, the pH value of the ionization is 0.1-0.3; the ionization temperature is 50-60 ℃; the ionization time is 0.1-2 h.
Preferably, the cathode of the acid wash three-stage electrolytic cyclone comprises the following steps: and mixing the cathode with acid, and washing and drying the obtained filter residue to obtain the palladium.
The invention provides a method for recovering palladium from biphenyl tetracarboxylic acid palladium-containing wastewater, which comprises the following steps: pretreating the biphenyl tetracarboxylic acid palladium-containing wastewater to obtain palladium ion-containing wastewater; enabling the palladium ion-containing wastewater to enter a three-stage electrolytic cyclone for electrolytic deposition, and pickling the cathode of the three-stage electrolytic cyclone to obtain palladium; the anode of the three-stage electrolytic cyclone comprises a titanium substrate and a platinum layer wrapped on the surface of the titanium substrate. According to the invention, the three-stage electrolytic cyclone is utilized to recover metal palladium, the anode active substance of the three-stage electrolytic cyclone is set to be metal platinum with the potential similar to that of palladium metal, so that reduction of palladium ions is facilitated, palladium is attached to a cathode in the form of a palladium simple substance, and recovery is simple; and flocculation precipitation cannot be caused in the electrolysis process, and no sludge solid waste is generated.
The data of the embodiment show that the recovery rate of palladium in the palladium-containing wastewater of the biphenyltetracarboxylic acid by the method is 98.9-99.01%.
Drawings
FIG. 1 is a top view of a three-stage electrolytic cyclone used in the present invention;
FIG. 2 is a cross-sectional view of a three-stage electrolytic cyclone used in the present invention;
wherein, 1 is a water inlet, 2 is a cylinder, 3 is an anode, 4 is an exhaust port, 5 is a water outlet, and 6 is a cathode.
Detailed Description
The invention provides a method for recovering palladium from biphenyl tetracarboxylic acid palladium-containing wastewater, which comprises the following steps:
pretreating the biphenyl tetracarboxylic acid palladium-containing wastewater to obtain palladium ion-containing wastewater;
enabling the palladium ion-containing wastewater to enter a three-stage electrolytic cyclone for electrolytic deposition, and pickling the cathode of the three-stage electrolytic cyclone to obtain palladium;
the anode of the three-stage electrolytic cyclone comprises a titanium substrate and a platinum layer wrapped on the surface of the titanium substrate.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention pretreats the biphenyl tetracarboxylic acid palladium-containing wastewater to obtain the palladium ion-containing wastewater.
In the present invention, the biphenyl tetracarboxylic acid palladium-containing wastewater is preferably palladium-containing wastewater generated in a coupling process in the production of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride. In the present invention, the biphenyltetracarboxylic acid palladium-containing wastewater preferably includes: 6-8 ppm of palladium, 0.2-0.5 wt% of BPTA, 0.5wt% of 4-chlorophthalic acid, 9wt% of sodium chloride and 8000 mg/L of COD.
In the present invention, the pretreatment preferably comprises the steps of:
removing organic matters from the biphenyl tetracarboxylic acid palladium-containing wastewater to obtain a mixed solution containing palladium and palladium ions;
ionizing the mixed solution containing palladium and palladium ions to obtain the palladium ion-containing wastewater.
In the present invention, the step of removing the organic matter preferably includes: and concentrating the biphenyl tetracarboxylic acid palladium-containing wastewater, adjusting the obtained concentrated wastewater to be acidic, and filtering to obtain the mixed solution containing palladium and palladium ions. In the present invention, the concentration is preferably a reduced pressure concentration, and the parameters of the reduced pressure concentration are not particularly limited as long as the biphenyltetracarboxylic acid palladium-containing wastewater can be concentrated to 30 to 50% of the original weight of the original liquid. In the invention, the pH value of the acidity is preferably 1-1.5, and more preferably 1.2-1.3; the reagent for adjusting the concentrated wastewater to be acidic preferably comprises hydrochloric acid; the concentration and volume of the hydrochloric acid are not particularly limited, as long as the pH value can be 1.0-1.5.
In the invention, the pH value of ionization is preferably 0.1-0.3; the pH adjusting agent preferably comprises nitric acid. In the invention, the ionization temperature is preferably 50-60 ℃, and more preferably 50-55 ℃. In the present invention, the time for the ionization is preferably 0.1 to 2 hours, and more preferably 1 to 2 hours.
In the present invention, the step of ionizing preferably comprises: adjusting the pH value of the mixed solution containing palladium and palladium ions, and heating to the ionization temperature for ionization.
According to the invention, the pH value of ionization is set to 0.1-0.3, the temperature is set to 50-60 ℃, the small palladium can be completely dissolved into palladium ions, and the recovery rate of palladium is improved.
After the ionization, the invention preferably further comprises adjusting the obtained ionized liquid to be alkaline; the pH value of the alkalinity is preferably 4-5. In the invention, the reagent for adjusting the obtained ionized liquid to be alkaline is preferably an inorganic base; the inorganic base preferably includes sodium hydroxide or potassium hydroxide, and more preferably sodium hydroxide.
In the invention, the ionized liquid is adjusted to be alkaline after ionization, so that the strong acidity of the palladium ion-containing wastewater can be avoided, and the service life of an electrode plate of the three-stage electrolytic cyclone is shortened.
In the invention, the content of palladium in the palladium ion-containing wastewater is preferably 15-25 ppm.
After the wastewater containing palladium ions is obtained, the wastewater containing palladium ions enters a three-stage electrolytic cyclone for electrolytic deposition, and the cathode of the three-stage electrolytic cyclone is pickled to obtain palladium.
In the invention, the three-stage electrolytic cyclones are communicated in series; according to the water flow direction, the three-stage electrolytic cyclone sequentially comprises a first electrolytic cyclone, a second electrolytic cyclone and a third electrolytic cyclone. In the present invention, a top view of the three-stage electrolytic cyclone is shown in FIG. 1, and a cross-sectional view of the three-stage electrolytic cyclone is shown in FIG. 2. As shown in fig. 1 and 2, the electrolytic cyclone comprises a water inlet 1, a cylinder 2, an anode 3, an exhaust port 4, a water outlet 5 and a cathode 6.
In the invention, the anode of the three-stage electrolytic cyclone comprises a titanium substrate and a platinum layer wrapped on the surface of the titanium substrate. In the present invention, the thickness of the platinum layer is preferably 20 to 100 μm, and more preferably 70 to 80 μm.
In the present invention, the material of the cathode preferably includes zinc, iron, or aluminum, and more preferably zinc. In the present invention, the cathode is preferably plate-shaped. In a particular embodiment of the invention, the cathode is preferably a zinc plate with a thickness of 0.5mm and a weight of 5 kg.
In the invention, in the electrolytic deposition process, the voltage of the three-stage electrolytic cyclone is preferably direct current voltage; the DC voltage is preferably 12-25V, and more preferably 12-13V. In the present invention, the dc voltage is preferably a rectangular wave voltage; the peak maximum value and the trough minimum value of the rectangular wave voltage are preferably 25V and 12V respectively; or the peak maximum value and the trough minimum value of the rectangular wave voltage are respectively 13V and 12V. In the present invention, the voltage pulse frequency of the rectangular wave voltage is preferably 20 to 35 kHz, and more preferably 20 to 25 kHz.
In the present invention, during the electrolytic deposition, the anode: 4OH--4e-═2H2O+O2×, cathode: pd2++2e→Pd；2H++2e→H2×) ×; i.e. palladium ions are charged to form palladium deposited on the cathode.
In the present invention, when the amount of water treated by the three-stage electrolytic cyclone is small, the amount of palladium deposited at the cathode is relatively small, and the cathode is not replaced temporarily. In the invention, the replacement cycle of the cathode of the first stage electrolytic cyclone of the three-stage electrolytic cyclones is preferably 20 to 25 tons of palladium ion-containing wastewater, and more preferably 20 tons of palladium ion-containing wastewater.
In the invention, the replacement period of the cathode of the second-stage electrolytic cyclone and the replacement period of the cathode of the third cyclone of the three-stage electrolytic cyclone are 200-500 tons of wastewater containing palladium ions independently.
After the lower cathode is replaced, the cathode of the three-stage electrolytic cyclone is acid-washed to obtain palladium.
In the invention, the cathode of the acid washing three-stage electrolytic cyclone comprises the following steps: and mixing the cathode with acid, and washing and drying the obtained filter residue to obtain the palladium.
In the present invention, the acid is preferably an inorganic acid, which preferably includes hydrochloric acid; the mass concentration of the hydrochloric acid is preferably 30%; the mass ratio of the hydrochloric acid with the mass concentration of 30% to the cathode is preferably 1: (3-6), more preferably 1: (4-4.5).
In the invention, the washing reagent is preferably water, and the amount of the water used in the invention is not particularly limited as long as the washing can be carried out until the pH value is 5-7. The temperature and time of the drying are not particularly limited as long as the drying of palladium can be achieved.
The following examples are provided to illustrate the method for recovering palladium from biphenyltetracarboxylic acid palladium-containing wastewater according to the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Detecting that the palladium content of 6t of the palladium-containing wastewater in the biphenyl tetracarboxylic acid workshop is 7.6 ppm, heating and concentrating at-0.09 MPa, extracting 3.3t of distilled water when the temperature of the kettle is 57 ℃ through reduced pressure concentration, and controlling the pH value of the residual liquid to be 5.9; adding 27 kg of 30wt% hydrochloric acid into the residual liquid to adjust the pH value to 1.2, then cooling the circulating water to 32 ℃, filtering the organic matter by a plate frame to obtain 43 kg of filtrate, and filtering the filtrate to obtain 2.55 t; adding 2.5kg of nitric acid into the filtrate to adjust the pH value to 0.2, then continuously heating to 55 ℃ for reaction for 1h, cooling to 32 ℃ after the reaction is finished, adding 9.5kg of sodium hydroxide to adjust the pH value to 4.2, and obtaining the wastewater containing palladium ions, wherein the palladium content is 18.2 ppm by detection.
Setting the rectangular voltage wave crest of the three-stage electrolytic cyclone to be 13V, the wave trough to be 12V and the voltage pulse frequency to be 25 kHz, starting to feed the wastewater containing palladium ions and electrifying, wherein the water inlet flow speed is 1 t/h, and after 2.5 h of water inlet, the water outlet detects that the palladium content is 0.04 ppm.
In the three-stage electrolytic cyclone, an anode comprises a titanium substrate and a platinum layer which is plated on the surface of the titanium substrate and has the thickness of 80 mu m; the cathode is a zinc plate with the thickness of 0.5mm, and the weight of the zinc plate is 5 kg; the parameters of the cathodes and the anodes of three electrolytic cyclones in the three-stage electrolytic cyclones are consistent.
After the cathode zinc plate was taken out, 20.2 kg of 30wt% hydrochloric acid was added thereto and stirred to dissolve the same, and the solid palladium was filtered to obtain 48.2 g, and then washed with 2kg of pure water to obtain 47.5 g of wet solid palladium, 45.15 g of dried palladium, and the palladium recovery rate was 99.01%.
Example 2
Detecting that the palladium content of 6t of the palladium-containing wastewater in the biphenyl tetracarboxylic acid workshop is 7.9 ppm, heating and concentrating under negative pressure of-0.093 MPa, extracting 3.4 t of distilled water when the temperature of a reduced pressure concentration kettle reaches 49 ℃, and keeping the pH value of the residual liquid at 5.8; adding 27 kg of 30wt% hydrochloric acid into the residual liquid to adjust the pH value to 1.19, then cooling the circulating water to 32 ℃, filtering the organic matter by a plate frame to obtain 43.2kg of organic matter, and filtering the filtrate for 2.45 t; adding 2.5kg of nitric acid into the filtrate to adjust the pH value to 0.18, then continuously heating to 55 ℃ for reaction for 1h, cooling to 32 ℃ after the reaction is finished, adding 9.6kg of sodium hydroxide to adjust the pH value to 4.4, obtaining the wastewater containing palladium ions, and detecting the palladium content to be 19.4 ppm.
Setting the rectangular voltage wave crest of the three-stage electrolytic cyclone to be 13V, the wave trough of the three-stage electrolytic cyclone to be 12V, setting the voltage pulse frequency to be 25 kHz, starting to feed the wastewater containing palladium ions and electrifying, wherein the water inlet flow rate is 1 t/h, and after 2.4 h, the water inlet is finished, and detecting the palladium content of 0.05 ppm in the discharged water.
The anode of the three-stage electrolytic cyclone comprises a titanium substrate and a platinum layer which is plated on the surface of the titanium substrate and has the thickness of 80 mu m; the cathode is a zinc plate with the thickness of 0.5mm, and the weight of the zinc plate is 5 kg; the parameters of the cathodes and the anodes of three electrolytic cyclones in the three-stage electrolytic cyclones are consistent.
The cathode zinc plate is taken out and added into 20.2 kg of 30% hydrochloric acid to be stirred and dissolved, solid palladium 50.2 g is obtained after filtration, wet solid palladium 49.5 g is obtained after top washing by using 2kg of pure water, and the recovery rate of palladium 46.9 g after drying is 98.9%.
Comparative example 1
Detecting that the palladium content of 6t of the palladium-containing wastewater in the biphenyl tetracarboxylic acid workshop is 7.2ppm, heating and concentrating under negative pressure of-0.093 MPa, extracting 3.3t of distilled water when the temperature of a reduced pressure concentration kettle reaches 49 ℃, adjusting the pH value of the residual liquid to 5.8, adding 26.5 kg of 30% hydrochloric acid to adjust the pH value to 1.23, then cooling the circulating water to 33 ℃, filtering 42.5kg of organic matters by a plate frame, and filtering 2.53t of filtrate; adding 2.5kg of nitric acid into the filtrate to adjust the pH value to 0.18, then continuously heating to 55 ℃ for reaction for 1h, cooling to 32 ℃ after the reaction is finished, adding 9.6kg of sodium hydroxide to adjust the pH value to 4.4, obtaining the wastewater containing palladium ions, and detecting the palladium content to be 17.2 ppm.
Setting the wave crest of rectangular voltage of the three-stage electrolytic cyclone to be 20V, the wave trough to be 0V and the voltage pulse frequency to be 20 kHz, starting to feed the wastewater containing palladium ions and electrifying, wherein the water inlet flow rate is 1 t/h, and after water inlet is finished after 2.4 h, discharging water and detecting the palladium content to be 7.5 ppm.
In the three-stage electrolytic cyclone, an anode comprises a titanium substrate and a platinum layer which is plated on the surface of the titanium substrate and has the thickness of 80 mu m; the cathode is a zinc plate with the thickness of 0.5mm, and the weight of the zinc plate is 5 kg; the parameters of the cathodes and the anodes of three electrolytic cyclones in the three-stage electrolytic cyclones are consistent.
The cathode zinc plate was taken out and dissolved in 20.2 kg of 30% hydrochloric acid under stirring, and then filtered to obtain 29.2 g of solid palladium, which was top-washed with 2kg of pure water to obtain 27.4 g of wet solid palladium, and the recovery rate of dried palladium (23.9 g) was 55.3%.
Comparative example 2
Detecting that the palladium content of 6t of the palladium-containing wastewater in the biphenyl tetracarboxylic acid workshop is 7.2ppm, heating and concentrating under negative pressure of-0.093 MPa, extracting 3.3t of distilled water when the temperature of a reduced pressure concentration kettle reaches 49 ℃, and keeping the pH value of the residual liquid at 5.8; adding 26.5 kg of 30% hydrochloric acid into the residual liquid to adjust the pH value to 1.23, then cooling the circulating water to 33 ℃, filtering organic matters by a plate frame by 42.5kg, and filtering the filtrate for 2.53 t; adding 1.6kg of sodium hydroxide into the filtrate to adjust the pH value to 4.4 to obtain the wastewater containing palladium ions, and detecting the content of the palladium ions to be 16.9 ppm.
And (3) setting the wave crest of the rectangular voltage of the three-stage electrolytic cyclone to be 13V, the wave trough to be 12V and the voltage pulse frequency to be 20 kHz, starting to feed the wastewater containing palladium ions and electrifying, wherein the water inlet flow rate is 1 t/h, and after 2.5 h of water inlet, finishing water inlet, and detecting the palladium content in the discharged water to be 8.5 ppm.
In the three-stage electrolytic cyclone, an anode comprises a titanium substrate and a platinum layer which is plated on the surface of the titanium substrate and has the thickness of 80 mu m; the cathode is a zinc plate with the thickness of 0.5mm, and the weight of the zinc plate is 5 kg; the parameters of the cathodes and the anodes of three electrolytic cyclones in the three-stage electrolytic cyclones are consistent.
The cathode zinc plate was taken out and dissolved in 20.2 kg of 30wt% hydrochloric acid under stirring, and then filtered to obtain 21.5 g of solid palladium, which was top-washed with 2kg of pure water to obtain 18.9 g of wet solid palladium, and the recovery rate of dried palladium (16.7 g) was 38.6%.
Comparative example 3
The differences from example 1 are: the platinum layer was replaced with a metallic ruthenium layer.
Detecting that the palladium content of 6t of the palladium-containing wastewater in the biphenyl tetracarboxylic acid workshop is 7.2ppm, heating and concentrating under negative pressure of-0.093 MPa, extracting 3.3t of distilled water when the temperature of a reduced pressure concentration kettle reaches 49 ℃, and keeping the pH value of the residual liquid at 5.8; adding 26.4 kg of 30% hydrochloric acid into the residual liquid to adjust the pH value to 1.24, then cooling the circulating water to 32 ℃, filtering the organic matter by a plate frame to obtain 43.2kg of organic matter, and filtering the filtrate for 2.53 t; adding 1.6kg of sodium hydroxide into the filtrate to adjust the pH value to 4.5 to obtain the wastewater containing palladium ions, and detecting the content of the palladium ions to be 16.8 ppm.
The wave crest of the rectangular voltage of the three-stage electrolytic cyclone is set to be 13V, the wave trough is set to be 12V, the voltage pulse frequency is set to be 20 kHz, the wastewater containing palladium ions starts to enter and is electrified, the inflow flow rate is 1 t/h, the water inflow is finished after 2.5 h, the palladium content of the effluent is 11.2 ppm, the strong sodium hypochlorite smell is generated in the recovery process, and the palladium ions in the water are not effectively recovered.
Comparative example 4
The differences from example 1 are: the thickness of the platinum layer was 10 μm.
Detecting that the palladium content of 6t of the palladium-containing wastewater in the biphenyl tetracarboxylic acid workshop is 7.9 ppm, heating and concentrating under negative pressure of-0.093 MPa, extracting 3.4 t of distilled water when the temperature of a reduced pressure concentration kettle reaches 48 ℃, and keeping the pH value of the residual liquid at 5.7; adding 27 kg of 30wt% hydrochloric acid into the residual liquid to adjust the pH value to 1.18, then cooling the circulating water to 32 ℃, filtering the organic matter by a plate frame to obtain 43.4 kg of organic matter, and filtering the filtrate for 2.45 t; adding 2.5kg of nitric acid into the filtrate to adjust the pH value to 0.17, then continuously heating to 55 ℃ for reaction for 1h, cooling to 32 ℃ after the reaction is finished, adding 9.7kg of sodium hydroxide to adjust the pH value to 4.4, obtaining the wastewater containing palladium ions, and detecting the palladium content to be 19.3 ppm.
Setting the rectangular voltage wave crest of the three-stage electrolytic cyclone to be 13V, the wave trough of the three-stage electrolytic cyclone to be 12V, setting the voltage pulse frequency to be 25 kHz, starting to feed the wastewater containing palladium ions and electrifying, wherein the water inlet flow rate is 1 t/h, and after 2.4 h, the water inlet is finished, and detecting the palladium content of 0.05 ppm in the discharged water.
The anode of the three-stage electrolytic cyclone comprises a titanium substrate and a platinum layer plated on the surface of the titanium substrate and having the thickness of 10 mu m; the cathode is a zinc plate with the thickness of 0.5mm, and the weight of the zinc plate is 5 kg; the parameters of the cathodes and the anodes of three electrolytic cyclones in the three-stage electrolytic cyclones are consistent.
The cathode zinc plate is taken out and added into 20.2 kg of 30% hydrochloric acid to be stirred and dissolved, solid palladium 50.2 g is obtained after filtration, wet solid palladium 49.5 g is obtained after top washing by using 2kg of pure water, and the recovery rate of palladium 46.8 g after drying is 98.7%.
After the recovery, the anode plate is inspected, slight corrosion pits are found on the surface, the anode cannot be normally used, and the service life of the anode is affected when the anode coating is thinner.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for recovering palladium from biphenyl tetracarboxylic acid palladium-containing wastewater comprises the following steps:
pretreating the biphenyl tetracarboxylic acid palladium-containing wastewater to obtain palladium ion-containing wastewater;
enabling the palladium ion-containing wastewater to enter a three-stage electrolytic cyclone for electrolytic deposition, and pickling the cathode of the three-stage electrolytic cyclone to obtain palladium;
the anode of the three-stage electrolytic cyclone comprises a titanium substrate and a platinum layer wrapped on the surface of the titanium substrate.
2. The method according to claim 1, wherein the thickness of the platinum layer is 20 to 100 μm.
3. The method of claim 1, wherein the cathode of the tertiary electrolytic cyclone comprises zinc, iron or aluminum.
4. The method according to claim 1, wherein during the electrolytic deposition, the voltage of the three-stage electrolytic cyclone is direct current voltage; the direct current voltage is 12-25V.
5. The method of claim 4, wherein the DC voltage is a square wave voltage.
6. The method according to claim 5, wherein the voltage pulse frequency of the rectangular wave voltage is 20 to 35 kHz.
7. The method according to claim 1, wherein the pre-processing comprises the steps of:
removing organic matters from the biphenyl tetracarboxylic acid palladium-containing wastewater to obtain a mixed solution containing palladium and palladium ions;
ionizing the mixed solution containing palladium and palladium ions to obtain the palladium ion-containing wastewater.
8. The method of claim 7, wherein the step of organic removal comprises: concentrating the biphenyl tetracarboxylic acid palladium-containing wastewater, adjusting the obtained concentrated wastewater to be acidic, and filtering to obtain the mixed solution containing palladium and palladium ions; the pH value of the acidity is 1-1.5.
9. The method according to claim 7, wherein the ionized pH value is 0.1-0.3; the ionization temperature is 50-60 ℃; the ionization time is 0.1-2 h.
10. The method of claim 1, wherein the cathode of the acid wash tertiary electrolytic cyclone comprises the steps of: and mixing the cathode with acid, and washing and drying the obtained filter residue to obtain the palladium.
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| CN115010601A (en) * | 2022-08-03 | 2022-09-06 | 河北海力香料股份有限公司 | Treatment method of 3,3',4,4' -biphenyltetracarboxylic acid production wastewater |
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| CN115010601A (en) * | 2022-08-03 | 2022-09-06 | 河北海力香料股份有限公司 | Treatment method of 3,3',4,4' -biphenyltetracarboxylic acid production wastewater |
| CN115010601B (en) * | 2022-08-03 | 2022-11-22 | 河北海力香料股份有限公司 | Method for treating 3,3',4,4' -biphenyl tetracarboxylic acid production wastewater |
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