Preparation of acid-resistant solid phase extraction filler and its application in the detection of PAM in copper electrolyte

Abstract

The present invention discloses a method for preparing an acid-resistant solid-phase extraction packing and its application in the detection of PAM in copper electrolyte. Weigh porous silica and disperse it in an aqueous HEMA solution, and obtain HEMA0 / SiO2 after evaporation and drying; after preparing the HEMA0 / SiO2 into an aqueous solution, disperse the porous silica in it and dry to obtain HEMA1 / SiO2; repeat the above several times to obtain silica microspheres HEMA n / SiO2, disperse it in anhydrous ethanol dissolved with HEMA, NVP, polyethylene glycol diacrylate and photoinitiator, and obtain the acid-resistant solid-phase extraction packing NVP-HEMA / HEMA n / SiO2 microspheres, then add them into DMF dissolved with 7-hydroxyheptanoic acid and EDC, and vacuum dry to obtain the solid-phase extraction packing HHA / NVP-HEMA / HEMA n / SiO2. This solid-phase extraction packing is applied to the detection of PAM in copper electrolyte. During detection, take the packing to fill the SPE column, establish a liquid chromatography detection method for PAM, and calculate the content of PAM in copper electrolysis. The packing has high adsorption efficiency and good stability. It eliminates the interference of copper ions and sulfuric acid in the actual sample, and has high detection accuracy.

Description

Technical Field

[0001] The invention relates to the technical field of wet smelting, in particular to a method for preparing an acid-resistant solid phase extraction filler and applying it to a detection method of PAM in a copper electrolyte. Background Art

[0002] In the process of copper electrolysis, traditional additives such as gelatin, casein, and thiourea are generally used to improve the quality of electrolytic copper. However, in the production process, the anode of the electrolytic cell produces anode mud during the electrolysis process. The anode mud floats on the upper part of the electrolytic cell and has poor fluidity. It will adhere to the upper mouth of the cathode copper, causing long particles on the upper edge of the cathode copper. The arsenic, antimony, bismuth and other metal elements contained in the cathode copper are mainly caused by the pollution of floating anode mud and the capillary pores between the crystals of the cathode sediment adsorbing the electrolyte containing arsenic, antimony, bismuth and other metal elements. Therefore, the presence of anode mud will seriously affect the appearance and chemical composition of the cathode copper. Due to the presence of floating anode mud, it is difficult to ensure the quality of copper electrolysis operations using only traditional additives.

[0003] The addition of the new additive cationic polyacrylamide can make the anode mud particles grow and then settle to the bottom of the tank or be filtered out by the filtration system, thereby eliminating the floating anode mud phenomenon and improving the granulation of cathode copper. Therefore, how to accurately detect the concentration of polyacrylamide is of great significance for the quality control of electrolytic cathode copper.

[0004] The technology for determining the concentration of polyacrylamide in conventional water samples is relatively mature, and common detection methods include starch-cadmium iodide colorimetry, turbidity, gel chromatography, chemiluminescence nitrogen determination, ammonia electrode method, etc. However, since the copper ion concentration in the copper electrolyte is as high as 40g / L and the sulfuric acid concentration is as high as 180g / L, it is a high-salt and high-acid sample. The background interference is serious when using colorimetry or turbidity to detect such samples, and direct use of chromatography to detect such samples will damage the chromatographic filler. Therefore, it is urgent to develop an effective detection method for polyacrylamide in copper electrolyte. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing an acid-resistant solid phase extraction filler and applying it to a detection method of PAM in a copper electrolyte, so as to eliminate the interference of copper ions and sulfuric acid in an actual sample and accurately detect the concentration of PAM in the copper electrolyte.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] A method for preparing an acid-resistant solid phase extraction filler comprises the following steps:

[0008] S1. Disperse porous silica in a HEMA aqueous solution with a mass concentration of 50-200 mg / L in an open beaker, the mass ratio of porous silica to HEMA aqueous solution is 50-200:1, heat to 60-80°C, stir, and obtain dry HEMA after all the water evaporates. 0 / SiO 2 ;

[0009] S2, HEMA prepared in S1 0 / SiO 2 Prepare HEMA again with a mass concentration of 50-200 mg / L 0 / SiO 2 The porous silica was then dispersed in HEMA in an open beaker. 0 / SiO 2 In aqueous solution, porous silica and HEMA 0 / SiO 2 The mass ratio of the aqueous solution is 50-200:1, heated to 60-80°C, stirred, and dried HEMA is obtained after all the water evaporates. 1 / SiO 2 ;

[0010] Repeat step S2 n times to obtain silica microspheres HEMA n / SiO 2 ;

[0011] S3, dissolving HEMA, NVP, polyethylene glycol diacrylate and photoinitiator in anhydrous ethanol at a mass ratio of 50-100:50-150:1-2:1 to obtain a mixed solution, wherein the concentration of HEMA in anhydrous ethanol is 500-1000 mg / L; taking silica microspheres HEMA n / SiO 2 Dispersed in the mixed solution, silica microspheres HEMA n / SiO 2 The mass ratio of HEMA is 20-60:1; stirring for 40-80 min under 365 nm ultraviolet light irradiation; after the reaction is completed, heating to evaporate the anhydrous ethanol solvent, adding deionized water to soak, washing, and vacuum drying to obtain NVP-HEMA / HEMA n / SiO 2 Microspheres;

[0012] S4, dissolving 7-hydroxyheptanoic acid and EDC in a mass ratio of 20-50:1 in DMF, wherein the concentration of 7-hydroxyheptanoic acid in DMF is 500-1000 mg / L; adding NVP-HEMA / HEMA prepared in step S3 n / SiO 2Microspheres, NVP-HEMA / HEMA n / SiO 2 The mass ratio of microspheres to 7-hydroxyheptanoic acid is 20:1-60:1; the product is obtained after heating to 70-100°C for 2-6 hours, and the product is centrifuged and washed alternately with ethanol and water, and vacuum dried to obtain a white powdery acid-resistant solid phase extraction filler HHA / NVP-HEMA / HEMA n / SiO 2 .

[0013] Preferably, the photoinitiator is Irgacure 2959.

[0014] Application of an acid-resistant solid phase extraction filler, the acid-resistant solid phase extraction filler is HHA / NVP-HEMA / HEMA prepared by the above method n / SiO 2 Filler, the acid-resistant solid phase extraction filler

[0015] HHA / NVP-HEMA / HEMA n / SiO 2 Applied to the detection of PAM in copper electrolyte.

[0016] A method for detecting PAM in copper electrolyte using an acid-resistant solid phase extraction filler, wherein the acid-resistant solid phase extraction filler is HHA / NVP-HEMA / HEMA prepared by the above method n / SiO 2 Filling, comprising the following steps:

[0017] Step 1: Weigh HHA / NVP-HEMA / HEMA n / SiO 2 30-50 mg of filler is loaded into an SPE column, and the SPE column is rinsed with 5-10 mL of methanol at a flow rate of 1 mL / min for activation, and then the SPE column is rinsed with 2-5 mL of copper electrolyte without PAM at a flow rate of 1 mL / min;

[0018] Step 2: Take 2-5 mL of the copper electrolyte sample containing PAM and pass it through the SPE column at a flow rate of 1 mL / min. After the water sample is extracted, rinse the SPE column with 2-5 mL of deionized water. After no liquid flows out, continue to pressurize to remove the residual water as much as possible, and then desorb the SPE column with 1 mL of eluent to obtain a concentrated sample of PAM. The eluent flow rate is 1 mL / min.

[0019] Step 3, prepare PAM standard solutions with concentrations of 5.0 mg / L, 10.0 mg / L, 20.0 mg / L, 30.0 mg / L and 50.0 mg / L;

[0020] Step 4: Use a diol-based chromatographic column to perform detection using molecular exclusion chromatography, inject the PAM standard solution prepared in step 3 into a high performance liquid chromatograph, pass through the diol-based chromatographic column, use an ultraviolet detector to perform detection, record the chromatogram, obtain the values ​​of retention time, peak height and peak area, and prepare a PAM standard curve;

[0021] Step 5: The PAM concentrated sample treated in step 2 is detected by molecular exclusion chromatography, the PAM concentrated sample is injected into a high performance liquid chromatograph, passed through a glycol-based chromatographic column, and detected using a UV detector, the chromatogram is recorded, the retention time, peak height and peak area values ​​are obtained, and the peak area values ​​corresponding to the relevant parameters are substituted into the standard curve to calculate the content of PAM in the copper electrolyte.

[0022] Preferably, the absorption wavelength of the ultraviolet detector is set to 200-205 nm.

[0023] Preferably, the mobile phase in the size exclusion chromatography is one of a sodium dihydrogen phosphate aqueous solution or an ammonium acetate aqueous solution, and the concentration of the mobile phase is 20-30 mmol / L.

[0024] Preferably, the length of the diol-based chromatographic column is 150-300 mm.

[0025] The acid-resistant solid phase extraction filler prepared by the present invention has high adsorption efficiency and good stability. By using the prepared solid phase extraction filler to fill the SPE column, the copper electrolyte sample containing PAM is pre-treated, and the PAM can be separated and concentrated from the copper electrolyte, which can effectively eliminate the background interference caused by the electrolyte and help to improve the detection limit. The PAM sample is detected by the exclusion chromatography method, which has high detection accuracy, high efficiency, and low equipment cost investment, and is suitable for popularization and application in the copper smelting industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The HHA / NVP-HEMA / HEMA prepared by the present invention n / SiO 2 Filler photos;

[0027] Figure 2 Chromatogram of PAM standard solution in Example 1;

[0028] Figure 3 is the chromatogram of the PAM concentrated sample in Example 1; DETAILED DESCRIPTION

[0029] The present invention is further described in detail below with reference to specific embodiments.

[0030] Example 1

[0031] A method for preparing an acid-resistant solid phase extraction filler comprises the following steps:

[0032] S1. Disperse porous silica in a 50 mg / L HEMA aqueous solution in an open beaker. The mass ratio of porous silica to HEMA aqueous solution is 50:1. Heat to 60°C and stir. After all the water evaporates, dry HEMA is obtained. 0 / SiO 2 ;

[0033] S2, HEMA prepared in S1 0 / SiO 2 Prepare HEMA again with a mass concentration of 50 mg / L 0 / SiO 2 The porous silica was then dispersed in HEMA in an open beaker. 0 / SiO 2 In aqueous solution, porous silica and HEMA 0 / SiO 2 The mass ratio of the aqueous solution is 50:1, heated to 60°C, stirred, and dried HEMA is obtained after all the water evaporates. 1 / SiO 2 ;

[0034] Repeat step S2 three times to obtain silica microspheres HEMA 3 / SiO 2 ;

[0035] S3, 50 mg HEMA, 50 mg NVP, 1 mg polyethylene glycol diacrylate and 1 mg photoinitiator were dissolved in 100 mL anhydrous ethanol to obtain a mixed solution, and 2.5 g silica microsphere HEMA was taken. 3 / SiO 2 Dispersed in the mixed solution, stirred for 40 min under 365 nm ultraviolet light; after the reaction, heated to evaporate the anhydrous ethanol solvent, added deionized water to soak, washed, and vacuum dried to obtain NVP-HEMA / HEMA 3 / SiO 2 microspheres; the photoinitiator is Irgacure 2959;

[0036] S4, dissolve 100 mg 7-hydroxyheptanoic acid and 5 mg EDC in 100 mL DMF, add NVP-HEMA / HEMA prepared in step S3 3 / SiO 2 2.5 g of microspheres were heated to 70 °C for 2 h to obtain the product; the product was centrifuged and washed alternately with ethanol and water, and vacuum dried to obtain a white powdery acid-resistant solid phase extraction filler HHA / NVP-HEMA / HEMA3 / SiO 2 .

[0037] Acid-resistant solid phase extraction filler HHA / NVP-HEMA / HEMA prepared by the above method 3 / SiO 2 , which can be applied to the detection of PAM in copper electrolyte.

[0038] HHA / NVP-HEMA / HEMA mentioned above 3 / SiO 2 The filler is applied to the detection method of PAM in copper electrolyte, comprising the following steps:

[0039] Step 1: Weigh HHA / NVP-HEMA / HEMA 3 / SiO 2 30 mg of filler was loaded into the SPE column, and the SPE column was rinsed with 5 mL of methanol at a flow rate of 1 mL / min for activation, and then the SPE column was rinsed with 2 mL of copper electrolyte without PAM at a flow rate of 1 mL / min;

[0040] Step 2: Take 2 mL of copper electrolyte sample containing PAM and pass it through the SPE column at a flow rate of 1 mL / min. After the water sample is extracted, rinse the SPE column with 2 mL of deionized water. After no liquid flows out, continue to pressurize to remove the residual water as much as possible, and then desorb the SPE column with 1 mL of eluent to obtain a concentrated sample of PAM. The eluent flow rate is 1 mL / min.

[0041] Step 3, prepare PAM standard solutions with concentrations of 5.0 mg / L, 10.0 mg / L, 20.0 mg / L, 30.0 mg / L and 50.0 mg / L;

[0042] Step 4: Use a diol-based chromatographic column to perform detection using molecular exclusion chromatography. Pipette the PAM standard solution prepared in step 3 and inject it into a high performance liquid chromatograph. Pass the diol-based chromatographic column and use an ultraviolet detector set at an absorption wavelength of 200 nm for detection. Record the chromatogram as shown in the figure. Figure 2 As shown, the values ​​of retention time, peak height and peak area were obtained to prepare a PAM standard curve; the retention time of PAM was 1.14 min, and the standard curve y=0.5781x-1.7633 was obtained based on the peak area calculation.

[0043] Step 5: Use molecular exclusion chromatography to detect the PAM concentrated sample after the treatment in step 2. Pipette the PAM concentrated sample and inject it into the high performance liquid chromatograph, pass it through the glycol-based chromatographic column, and use the ultraviolet detector to detect it. Record the chromatogram as follows: Figure 3As shown, the peak height and peak area values ​​were obtained, and the corresponding parameters of the peak area values ​​were substituted into the standard curve to calculate the content of PAM in the copper electrolyte to be 5.88 mg / L.

[0044] The mobile phase in the above-mentioned molecular exclusion chromatography is sodium dihydrogen phosphate aqueous solution, the concentration of the mobile phase is 25 mol / L, the length of the diol-based chromatographic column is 250 mm, and the flow rate of the high performance liquid chromatograph is 1.0 mL / min.

[0045] Example 2

[0046] A method for preparing an acid-resistant solid phase extraction filler comprises the following steps:

[0047] S1. Disperse porous silica in a 200 mg / L HEMA aqueous solution in an open beaker. The mass ratio of porous silica to HEMA aqueous solution is 200:1. Heat to 80°C and stir. After all the water evaporates, dry HEMA is obtained. 0 / SiO 2 ;

[0048] S2, HEMA prepared in S1 0 / SiO 2 Prepare HEMA again with a mass concentration of 200 mg / L 0 / SiO 2 The porous silica was then dispersed in HEMA in an open beaker. 0 / SiO 2 In aqueous solution, porous silica and HEMA 0 / SiO 2 The mass ratio of the aqueous solution is 200:1, heated to 80°C, stirred, and dried HEMA is obtained after all the water evaporates. 1 / SiO 2 ;

[0049] Repeat step S2 four times to obtain silica microspheres HEMA 4 / SiO 2 ;

[0050] S3, 100 mg HEMA, 150 mg NVP, 2 mg polyethylene glycol diacrylate and 1 mg photoinitiator were dissolved in 100 mL anhydrous ethanol to obtain a mixed solution, 2.5 g silica microsphere HEMA 4 / SiO 2 Dispersed in the mixed solution, stirred for 80 min under 365 nm ultraviolet irradiation; after the reaction, heated to evaporate the anhydrous ethanol solvent, added deionized water to soak, washed, and vacuum dried to obtain NVP-HEMA / HEMA 4 / SiO2 microspheres; the photoinitiator is Irgacure 2959;

[0051] S4, 80 mg of 7-hydroxyheptanoic acid and 1 mg of EDC were dissolved in 100 mL of DMF, and the NVP-HEMA / HEMA prepared in step S3 was added. 4 / SiO 2 2.5 g of microspheres were heated to 100 °C for 6 h to obtain the product; the product was centrifuged and washed alternately with ethanol and water, and vacuum dried to obtain a white powdery acid-resistant solid phase extraction filler HHA / NVP-HEMA / HEMA 4 / SiO 2 .

[0052] HHA / NVP-HEMA / HEMA prepared by the above method 4 / SiO 2 Filler can be used for the detection of PAM in copper electrolyte.

[0053] HHA / NVP-HEMA / HEMA mentioned above 4 / SiO 2 The method for detecting PAM in copper electrolyte using filler comprises the following steps:

[0054] Step 1: Weigh HHA / NVP-HEMA / HEMA 4 / SiO 2 50 mg of filler was loaded into an SPE column, and the SPE column was activated by flushing with 10 mL of methanol at a flow rate of 1 mL / min, and then flushing the SPE column with 5 mL of copper electrolyte without PAM at a flow rate of 1 mL / min;

[0055] Step 2: Take 5 mL of the copper electrolyte sample containing PAM and pass it through the SPE column at a flow rate of 1 mL / min. After the water sample is extracted, rinse the SPE column with 5 mL of deionized water. After no liquid flows out, continue to pressurize to remove the residual water as much as possible, and then desorb the SPE column with 1 mL of eluent to obtain a concentrated sample of PAM. The eluent flow rate is 1 mL / min.

[0056] Step 3, prepare PAM standard solutions with concentrations of 5.0 mg / L, 10.0 mg / L, 20.0 mg / L, 30.0 mg / L and 50.0 mg / L;

[0057] Step 4: Use a diol-based chromatographic column to perform detection by molecular exclusion chromatography, inject the PAM standard solution prepared in step 3 into a high performance liquid chromatograph, pass through a diol-based chromatographic column, and perform detection using a UV detector. Record the chromatogram, obtain the values ​​of retention time, peak height, and peak area, and prepare a PAM standard curve; the retention time of polyacrylamide is 1.14 min, and the standard curve y=0.5781x-1.7633 is calculated based on the peak area;

[0058] Step 5: The PAM concentrated sample treated in step 2 is detected by molecular exclusion chromatography, the PAM concentrated sample is injected into a high performance liquid chromatograph, passed through a glycol-based chromatographic column, and detected using a UV detector, the chromatogram is recorded, the retention time, peak height and peak area values ​​are obtained, and the peak area values ​​corresponding to the relevant parameters are substituted into the standard curve, and the PAM content in the copper electrolyte is calculated to be 5.73 mg / L.

[0059] The absorption wavelength of the UV detector was set to 205 nm; the mobile phase in the size exclusion chromatography was an aqueous solution of ammonium acetate, and the concentration of the mobile phase was 30 mmol / L; the length of the diol-based chromatographic column was 150 mm; and the flow rate of the HPLC was 0.8 mL / min.

[0060] Example 3

[0061] A method for preparing an acid-resistant solid phase extraction filler comprises the following steps:

[0062] S1. Disperse porous silica in a 100 mg / L HEMA aqueous solution in an open beaker. The mass ratio of porous silica to HEMA aqueous solution is 100:1. Heat to 70°C and stir. After all the water evaporates, dry HEMA is obtained. 0 / SiO 2 ;

[0063] S2, HEMA prepared in S1 0 / SiO 2 Prepare HEMA again with a mass concentration of 100 mg / L 0 / SiO 2 The porous silica was then dispersed in HEMA in an open beaker. 0 / SiO 2 In aqueous solution, porous silica and HEMA 0 / SiO 2 The mass ratio of the aqueous solution is 100:1, heated to 70°C, stirred, and dried HEMA is obtained after all the water evaporates. 1 / SiO 2 ;

[0064] Repeat step S2 five times to obtain silica microspheres HEMA 5 / SiO 2 ;

[0065] S3, 70 mg HEMA, 100 mg NVP, 1.5 mg polyethylene glycol diacrylate and 1 mg photoinitiator were dissolved in 100 mL anhydrous ethanol to obtain a mixed solution, 2.0 g silica microsphere HEMA 5 / SiO 2 Dispersed in the mixed solution, stirred for 60 min under 365 nm ultraviolet light irradiation; after the reaction, heated to evaporate the anhydrous ethanol solvent, added deionized water to soak, washed, and vacuum dried to obtain NVP-HEMA / HEMA 5 / SiO 2 microspheres; the photoinitiator is Irgacure 2959;

[0066] S4, 50 mg 7-hydroxyheptanoic acid and 1 mg EDC were dissolved in 100 mL DMF, and the NVP-HEMA / HEMA prepared in step S3 was added. 5 / SiO 2 2.0 g of microspheres were heated to 80 °C for 4 h to obtain the product; the product was centrifuged and washed alternately with ethanol and water, and vacuum dried to obtain a white powdery acid-resistant solid phase extraction filler HHA / NVP-HEMA / HEMA 5 / SiO 2 .

[0067] HHA / NVP-HEMA / HEMA prepared by the above method 5 / SiO 2 Filler can be used for the detection of PAM in copper electrolyte.

[0068] HHA / NVP-HEMA / HEMA mentioned above 5 / SiO 2 The method for detecting PAM in copper electrolyte using fillers includes the following steps:

[0069] Step 1: Weigh HHA / NVP-HEMA / HEMA 5 / SiO 2 40 mg of filler was loaded into an SPE column, and the SPE column was activated by flushing with 7 mL of methanol at a flow rate of 1 mL / min, and then flushing the SPE column with 4 mL of copper electrolyte without PAM at a flow rate of 1 mL / min;

[0070] Step 2: Take 4 mL of the copper electrolyte sample containing PAM and pass it through the SPE column at a flow rate of 1 mL / min. After the water sample is extracted, rinse the SPE column with 4 mL of deionized water. After no liquid flows out, continue to pressurize to remove the residual water as much as possible, and then desorb the SPE column with 1 mL of eluent to obtain a concentrated sample of PAM. The eluent flow rate is 1 mL / min.

[0071] Step 3, prepare PAM standard solutions with concentrations of 5.0 mg / L, 10.0 mg / L, 20.0 mg / L, 30.0 mg / L and 50.0 mg / L;

[0072] Step 4: Use a diol-based chromatographic column to perform detection by molecular exclusion chromatography, inject the PAM standard solution prepared in step 3 into a high performance liquid chromatograph, pass through a diol-based chromatographic column, and perform detection using a UV detector. Record the chromatogram, obtain the values ​​of retention time, peak height, and peak area, and prepare a PAM standard curve; the retention time of polyacrylamide is 1.14 min, and the standard curve y=0.5781x-1.7633 is calculated based on the peak area;

[0073] Step 5: The PAM concentrated sample treated in step 2 is detected by molecular exclusion chromatography, the PAM concentrated sample is injected into a high performance liquid chromatograph, passed through a glycol-based chromatographic column, and detected using a UV detector, the chromatogram is recorded, the retention time, peak height and peak area values ​​are obtained, and the peak area values ​​corresponding to the relevant parameters are substituted into the standard curve, and the PAM content in the copper electrolyte is calculated to be 5.92 mg / L.

[0074] The absorption wavelength of the UV detector was set to 200 nm; the mobile phase in the size exclusion chromatography was sodium dihydrogen phosphate aqueous solution, and the concentration of the mobile phase was 20 mmol / L; the length of the diol-based chromatographic column was 300 mm; and the flow rate of the high performance liquid chromatograph was 1.0 mL / min.

[0075] The filler prepared by the invention has high adsorption efficiency and good stability. When applied to PAM detection in copper electrolyte, the interference of copper ions and sulfuric acid in the actual sample is eliminated, and the detection accuracy is high.

[0076] The above are only preferred embodiments of the present invention. It should be noted that for those skilled in the art, under the technical enlightenment provided by the present invention, other equivalent variations and improvements can also be made, which should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing an acid-resistant solid phase extraction filler, Features: The following steps are involved: S1. Disperse porous silica in a HEMA aqueous solution with a mass concentration of 50-200 mg / L in an open beaker, the mass ratio of porous silica to HEMA aqueous solution is 50-200:1, heat to 60-80°C, stir, and obtain dry HEMA after all the water evaporates. 0 / SiO 2 ; S2, HEMA prepared in S1 0 / SiO 2 Prepare HEMA again with a mass concentration of 50-200 mg / L 0 / SiO 2 The porous silica was then dispersed in HEMA in an open beaker. 0 / SiO 2 In aqueous solution, porous silica and HEMA 0 / SiO 2 The mass ratio of the aqueous solution is 50-200:1, heated to 60-80°C, stirred, and dried HEMA is obtained after all the water evaporates. 1 / SiO 2 ; Repeat step S2 n times to obtain silica microspheres HEMA n / SiO 2 ; S3, dissolving HEMA, NVP, polyethylene glycol diacrylate and photoinitiator in anhydrous ethanol at a mass ratio of 50-100:50-150:1-2:1 to obtain a mixed solution, wherein the concentration of HEMA in anhydrous ethanol is 500-1000 mg / L; taking silica microspheres HEMA n / SiO 2 Dispersed in the mixed solution, silica microspheres HEMA n / SiO 2 The mass ratio of HEMA is 20-60:1; stirring for 40-80 min under 365 nm ultraviolet light irradiation; after the reaction is completed, heating to evaporate the anhydrous ethanol solvent, adding deionized water to soak, washing, and vacuum drying to obtain NVP-HEMA / HEMA n / SiO 2 Microspheres; S4, dissolving 7-hydroxyheptanoic acid and EDC in a mass ratio of 20-50:1 in DMF, wherein the concentration of 7-hydroxyheptanoic acid in DMF is 500-1000 mg / L; adding NVP-HEMA / HEMA prepared in step S3 n / SiO 2 Microspheres, NVP-HEMA / HEMA n / SiO 2 The mass ratio of microspheres to 7-hydroxyheptanoic acid is 20:1-60:1; the product is obtained after heating to 70-100°C for 2-6 hours, and the product is centrifuged and washed alternately with ethanol and water, and vacuum dried to obtain a white powdery acid-resistant solid phase extraction filler HHA / NVP-HEMA / HEMA n / SiO 2 .

2. The method for preparing the acid-resistant solid phase extraction filler according to claim 1, Features: The photoinitiator is Irgacure 2959.

3. Application of an acid-resistant solid phase extraction filler, the acid-resistant solid phase extraction filler is HHA / NVP-HEMA / HEMA prepared according to the method of claim 2 n / SiO 2 filler, Features: The acid-resistant solid-phase extraction packing HHA / NVP-HEMA / HEMA n / SiO 2 is applied to the detection of PAM in copper electrolyte solution.

4. A method for detecting PAM in copper electrolyte using an acid-resistant solid phase extraction filler, wherein the acid-resistant solid phase extraction filler is HHA / NVP-HEMA / HEMA prepared according to the method of claim 2 n / SiO 2 filler, Features: The following steps are involved: Step 1: Weigh HHA / NVP-HEMA / HEMA n / SiO 2 30-50 mg of filler is loaded into an SPE column, and the SPE column is rinsed with 5-10 mL of methanol at a flow rate of 1 mL / min for activation, and then the SPE column is rinsed with 2-5 mL of copper electrolyte without PAM at a flow rate of 1 mL / min; Step 2: Take 2-5 mL of the copper electrolyte sample containing PAM and pass it through the SPE column at a flow rate of 1 mL / min. After the water sample is extracted, rinse the SPE column with 2-5 mL of deionized water. After no liquid flows out, continue to pressurize to remove the residual water as much as possible, and then desorb the SPE column with 1 mL of eluent to obtain a concentrated sample of PAM. The eluent flow rate is 1 mL / min. Step 3, prepare PAM standard solutions with concentrations of 5.0 mg / L, 10.0 mg / L, 20.0 mg / L, 30.0 mg / L and 50.0 mg / L; Step 4: Use a diol-based chromatographic column to perform detection using molecular exclusion chromatography, inject the PAM standard solution prepared in step 3 into a high performance liquid chromatograph, pass through the diol-based chromatographic column, use an ultraviolet detector to perform detection, record the chromatogram, obtain the values ​​of retention time, peak height and peak area, and prepare a PAM standard curve; Step 5: The PAM concentrated sample treated in step 2 is detected by molecular exclusion chromatography, the PAM concentrated sample is injected into a high performance liquid chromatograph, passed through a glycol-based chromatographic column, and detected using a UV detector, the chromatogram is recorded, the retention time, peak height and peak area values ​​are obtained, and the peak area values ​​corresponding to the relevant parameters are substituted into the standard curve to calculate the content of PAM in the copper electrolyte.

5. The detection method according to claim 4, Features: The absorption wavelength of the ultraviolet detector is set to 200-205 nm.

6. The detection method according to claim 4 or 5, Features: The mobile phase in the molecular exclusion chromatography is one of a sodium dihydrogen phosphate aqueous solution or an ammonium acetate aqueous solution, and the concentration of the mobile phase is 20-30 mmol / L.

7. The detection method according to claim 6, Features: The length of the diol-based chromatographic column is 150-300 mm.

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