A method for grading treatment and resource utilization of high-strength steel pickling waste liquid based on chromium-nickel double-template molecular imprinting adsorbent
The graded treatment process using chromium-nickel dual-template molecularly imprinted adsorbents solved the problem of separating and recovering Cr3+ and Ni2+ in high-strength steel pickling wastewater, achieving efficient resource utilization and environmentally friendly treatment, while reducing costs and complexity.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- BENGANG STEEL PLATES CO LTD
- Filing Date
- 2026-06-11
- Publication Date
- 2026-07-14
AI Technical Summary
Existing technologies are insufficient to effectively separate and recover Cr3+ and Ni2+ from pickling waste liquid of high-strength steel, resulting in the underutilization of resources. Furthermore, conventional adsorption methods require a large area, are costly, and involve complex processes.
Hollow polymer microspheres with a particle size of 50–200 μm were prepared by using a chromium-nickel dual-template molecularly imprinted adsorbent and through a process involving pretreatment, nanofiltration, adsorption and desorption in a primary adsorption column, and adsorption and desorption in a secondary adsorption column, thereby achieving synergistic adsorption and gradient desorption of Cr3+ and Ni2+.
It achieves efficient separation and recovery of Cr3+ and Ni2+, prepares chromium-nickel composite oxide, utilizes resources, and allows the adsorbent to be recycled, meeting green and environmental protection requirements while reducing costs and complexity.
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Figure CN122380602A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of metallurgical wastewater resource treatment technology, specifically relating to a method for graded treatment and resource utilization of high-strength steel pickling waste liquid based on chromium-nickel dual-template molecularly imprinted adsorbent. Background Technology
[0002] High-strength steel has a complex alloy composition, typically containing multiple alloying elements such as Cr, Ni, Mo, Cu, Nb, V, and Ti. During pickling, the alloying elements on the steel plate surface, along with iron oxide scale, enter the pickling solution, forming a mixture containing Fe. 3+ Cr 3+ Ni 2+ Cu 2+ And a complex waste liquid system containing various trace alloy ions, including Cr 3+ and Ni 2+ Their physicochemical properties are similar, and it is difficult to achieve effective separation using conventional adsorption or precipitation methods, which makes it difficult to better recycle and utilize these metal resources.
[0003] Molecular imprinting is a novel separation technique that involves pretreatment, site preparation, polymerization, and elution. This process leaves cavities within the polymer that are identical to the substances to be separated. These cavities can then be used to selectively adsorb the desired substances. For example, multiple recognition sites can be simultaneously established within the same polymer, enabling the synergistic separation of multiple target analytes.
[0004] Currently, the main technologies for treating pickling wastewater include neutralization precipitation, calcination, membrane separation, resin adsorption, and molecularly imprinted adsorption. Among these, molecularly imprinted adsorption technology, with its high specificity and selectivity, good stability, flexible preparation process, low cost, and wide applicability, shows great application potential and value in the field of pickling wastewater treatment. Existing technologies mainly target organic matter or heavy metals with significantly different properties, and can only selectively adsorb single metal ions. When treating complex wastewater containing multiple metals, multiple adsorption columns need to be connected in series, resulting in large footprints, high costs, and complex processes. In pickling wastewater treatment, existing technologies are mostly single-method approaches, lacking a complete system for recovery, separation, and product preparation, and thus have limited resource utilization.
[0005] Therefore, there is an urgent need to develop a multi-element adsorbent with good selectivity for the treatment of pickling waste liquid, and to construct an integrated treatment method for recycling, separation and product resource utilization. Summary of the Invention
[0006] Therefore, the purpose of this invention is to provide a method for graded treatment and resource utilization of high-strength steel pickling waste liquid based on chromium-nickel dual-template molecularly imprinted adsorbent.
[0007] To achieve the above objectives, the present invention provides the following technical solution:
[0008] In a first aspect, the present invention provides a method for graded treatment and resource utilization of high-strength steel pickling waste liquid based on chromium-nickel dual-template molecularly imprinted adsorbent, including a process flow of pickling waste liquid pretreatment, nanofiltration, adsorption and desorption by a primary adsorption column, and adsorption and desorption by a secondary adsorption column. The secondary adsorption column is packed with the chromium-nickel dual-template molecularly imprinted adsorbent, which is a hollow polymer microsphere with a particle size of 50-200 μm, and is prepared by the following method: Aqueous phase was prepared by dissolving the dispersant in deionized water; chromium and nickel salts were mixed and dissolved in an organic solvent to prepare a template ion solution, followed by the addition of 4-vinylpyridine, ethylene glycol dimethacrylate, and azobisisobutyronitrile, along with a pore-forming agent, and ultrasonically dispersed to prepare an oil phase; the oil phase was slowly added to the aqueous phase under stirring, and an inert gas was introduced to remove oxygen for 10-20 min, the temperature was raised to 60-80℃, and the polymerization reaction was carried out for 12-24 h; after the reaction, the polymer microspheres were separated, template ions were eluted, washed, and vacuum dried to obtain the chromium-nickel dual-template molecularly imprinted adsorbent.
[0009] Based on the above technical solution, further, the high-strength steel pickling waste liquid is pickling waste liquid of high-strength steel treated with sulfuric acid-hydrochloric acid mixed acid or pickling waste liquid of high-strength steel treated with hydrochloric acid. The mixed acid pickling waste liquid has the following composition: sulfuric acid 2%~5%, hydrochloric acid 1%~4%, iron 15~20 g / L, chromium 0.4~0.9 g / L, and nickel 0.3~0.6 g / L; the hydrochloric acid pickling waste liquid has the following composition: hydrochloric acid 4%~8%, iron 12~20 g / L, chromium 0.5~0.9 g / L, and nickel 0.2~0.6 g / L.
[0010] Based on the above technical solution, the dispersant is further selected from one or more of polyvinyl alcohol, gelatin or hydroxyethyl cellulose, and the mass fraction of the dispersant is 1% to 5%.
[0011] Based on the above technical solution, the molar ratio of the chromium salt to the nickel salt is further 1:2 to 2:1.
[0012] Based on the above technical solution, the molar ratio of the template ion to 4-vinylpyridine is further 1:3 to 1:8.
[0013] Based on the above technical solution, the molar ratio of 4-vinylpyridine to ethylene glycol dimethacrylate is further 1:2 to 1:6.
[0014] Based on the above technical solution, the amount of azobisisobutyronitrile used is 1% to 3% of the mass of 4-vinylpyridine.
[0015] Based on the above technical solution, the pore-forming agent is toluene or cyclohexane, and the amount used is 20% to 50% of the mass of 4-vinylpyridine.
[0016] Based on the above technical solution, the volume ratio of the oil phase to the water phase is further 1:3 to 1:5.
[0017] Based on the above technical solution, the stirring speed is further 200~800 revolutions per minute.
[0018] Based on the above technical solution, the template ions are further eluted using a methanol-acetic acid mixed solution, wherein the volume ratio of methanol to acetic acid is 9:1 to 7:3, and the elution time is 24 to 48 hours.
[0019] Based on the above technical solution, the adsorption process of the secondary adsorption column is further as follows: the pH of the effluent from the primary adsorption column is adjusted to 3.0~4.0, and the effluent enters the secondary adsorption column at 1~3 BV / h, and adsorbs at 30~45℃ for 4~8 h to saturate.
[0020] Based on the above technical solution, the desorption process of the secondary adsorption column is further as follows: Ni is eluted with 0.1~0.3 mol / L HCl. 2+ The elution rate was 0.5–1.0 BV / h, and the elution volume was 1–3 BV, yielding a nickel-rich solution; Cr was eluted with 1.0–2.0 mol / L HCl. 3+ The elution rate was 1~2 BV / h, and the elution volume was 2~4 BV, to obtain a chromium-enriched solution.
[0021] Based on the above technical solution, the method for utilizing the nickel enrichment solution and the chromium enrichment solution is to adjust the pH of the enrichment solution to 8.0~9.0, allow the precipitation reaction to proceed for 1~2 hours, filter and wash, and then calcine at 800~1000℃ for 2~4 hours to obtain nickel oxide and / or chromium oxide.
[0022] Compared with the prior art, the present invention has the following beneficial effects: 1. The chromium-nickel dual-template molecularly imprinted adsorbent of the present invention produces no secondary pollution during the entire wastewater treatment process, which meets the requirements of circular economy and green development. The high selectivity adsorption can realize the separation, recovery and reuse of heavy metals in wastewater, thus achieving resource utilization.
[0023] 2. The adsorbent prepared by this invention can achieve synergistic adsorption of chromium and nickel ions. 3+ and Ni 2+ The presence of imprinted cavities creates a synergistic effect, enhancing the overall recognition capability of the adsorbent material.
[0024] 3. The chromium-nickel dual-template molecularly imprinted adsorbent of the present invention has good adsorption selectivity, and the adsorbent has good adsorption selectivity for Cr. 3+and Ni 2+ It can selectively and efficiently adsorb, but has weak adsorption capacity for other metal ions.
[0025] 4. The chromium-nickel dual-template molecularly imprinted adsorbent of the present invention can achieve gradient desorption. By utilizing the difference in binding strength between chromium and nickel and the site, chromium and nickel ions are obtained by desorption with hydrochloric acid of different concentrations, and then prepared into chromium-nickel composite oxides for recycling.
[0026] 5. The chromium-nickel dual-template molecularly imprinted adsorbent of the present invention has good durability and can be used in an adsorption-desorption cycle, showing good prospects for industrial application. Attached Figure Description
[0027] To more clearly illustrate the embodiments of the present invention, the accompanying drawings involved in the embodiments will be briefly described below.
[0028] Figure 1 This is a flowchart illustrating the preparation process of the chromium-nickel dual-template molecularly imprinted adsorbent of the present invention.
[0029] Figure 2 The adsorption kinetics curve of the chromium-nickel dual-template molecularly imprinted adsorbent prepared in this invention.
[0030] Figure 3 This is a process flow diagram of the graded treatment and resource utilization method for high-strength steel pickling waste liquid of the present invention.
[0031] Figure 4 This is a flow chart of nanofiltration in the graded treatment and resource utilization method of high-strength steel pickling waste liquid of the present invention.
[0032] Figure 5 This is a flowchart of the desorption of the first-stage adsorption column and the reuse of iron ions in the graded treatment and resource utilization method of high-strength steel pickling waste liquid of the present invention.
[0033] Figure 6 This is a flowchart of the secondary adsorption column desorption and chromium and nickel ion reuse process in the graded treatment and resource utilization method of high-strength steel pickling waste liquid of the present invention. Detailed Implementation
[0034] The present invention will be described in detail below with reference to the embodiments. However, the implementation of the present invention is not limited thereto. Obviously, the embodiments described below are only some embodiments of the present invention. For those skilled in the art, other similar embodiments can be obtained without creative effort and all fall within the protection scope of the present invention.
[0035] Example 1: Preparation of Chromium-Nickel Dual-Template Molecularly Imprinted Adsorbent (1) Aqueous phase preparation: Weigh 6 g of polyvinyl alcohol (degree of polymerization 1700, degree of alcoholysis 88%), add it to 200 mL of deionized water, heat to 80℃ and stir to dissolve, then cool to room temperature for later use.
[0036] (2) Preparation of oil phase: Dissolve 34.0 g of Cr(NO3) and 22.9 g of Ni(NO3) in 100 mL of methanol, add 12.6 g of 4-vinylpyridine, 23.7 g of ethylene glycol dimethacrylate and 0.4 g of azobisisobutyronitrile, add 3.78 mL of toluene, and sonicate for 10 minutes to form oil phase.
[0037] (3) Suspension polymerization: The oil phase was slowly added to the aqueous phase while stirring at 400 rpm, and deionized water was added to bring the total volume to 400 mL. Nitrogen was purged for 15 min to remove oxygen, and the mixture was sealed and heated to 70 °C for 18 h. After the reaction, the supernatant was removed, and the polymer microspheres were washed three times with hot water at 60 °C. The mixture was then filtered and dried at 60 °C for 12 h.
[0038] (4) Template elution: The dried microspheres were loaded into a Soxhlet extractor and extracted with methanol-acetic acid (9:1) solution for 48 h. The microspheres were then washed with methanol until neutral and dried under vacuum at 60 °C for 24 h to obtain chromium-nickel dual-template molecularly imprinted adsorbent microspheres with a particle size of 80-120 μm.
[0039] Example 2: Adsorption performance study of chromium-nickel dual-template molecularly imprinted adsorbent The adsorption performance was investigated by changing the template ion ratio, the ratio of template ions to functional monomer 4-vinylpyridine, and the ratio of functional monomer 4-vinylpyridine to crosslinking agent ethylene glycol dimethacrylate.
[0040] (1) Selection of template ion ratio Adsorbents with different template ion ratios were prepared by setting the molar ratio of Cr(NO3)3 to Ni(NO3)2 to 1:0, 2:1, 1:1, 1:2, and 0:1, respectively, with the remaining steps being the same as in Example 1. 0.1 g of the prepared adsorbent was then added to the Cr-containing... 3+ 50 mg / L and Ni 2+ Adsorption was performed using 50 mL of a 50 mg / L mixed solution (pH=3.5) at 25℃ with shaking for 4 h. The 1:0 group was for Cr... 3+ Single-template adsorbent; group 0:1 is Ni 2+ Single-template adsorbent.
[0041] After the reaction is complete, Cr 3+ Adsorption capacity and Ni 2+ The adsorption capacity is shown in Table 1. Table 1 shows that the adsorption effect is best when the chromium-nickel ion ratio is 1:1; the dual-template adsorbent can achieve Cr...3+ with Ni 2+ It exhibits dual adsorption, and its adsorption effect is superior to that of single-template adsorbents.
[0042] Table 1 Template Ion Ratio
[0043] (2) Selection of the ratio of template ion to 4-vinylpyridine The molar ratio of template ion to 4-vinylpyridine was set to 1:3, 1:4, 1:5, 1:6, 1:7, and 1:8, respectively. The remaining steps were the same as in Example 1. 0.1 g of the prepared adsorbent was taken and Cr-containing... 3+ 50 mg / L and Ni 2+ Adsorption was performed by shaking 50 mL of a 50 mg / L mixture (pH=3.5) at 25°C for 4 h.
[0044] The results are shown in Table 2. As can be seen from the table, when the molar ratio of template ion to 4-vinylpyridine is 1:4 to 1:8, the adsorption effect is very good. Among them, the adsorption amount is higher and the value is relatively stable when the ratio is 1:6 to 1:8. Considering all factors, the molar ratio of template ion to 4-vinylpyridine is 1:6, which is economical and practical.
[0045] Table 2. Ratio of template ion to 4-vinylpyridine
[0046] (3) Selection of the ratio of 4-vinylpyridine to ethylene glycol dimethacrylate The molar ratios of the functional monomer 4-vinylpyridine to the crosslinking agent ethylene glycol dimethacrylate were set to 1:2, 1:3, 1:4, 1:5, and 1:6, respectively. The remaining steps were the same as in Example 1. 0.1 g of the prepared adsorbent was taken and Cr-containing... 3+ 50 mg / L and Ni 2+ Adsorption was performed by shaking 50 mL of a 50 mg / L mixture (pH=3.5) at 25°C for 4 h.
[0047] The results are shown in Table 3. As can be seen from the table, the adsorption effect is best when the ratio of functional monomer 4-vinylpyridine to crosslinking agent ethylene glycol dimethacrylate is 1:4.
[0048] Table 3 Ratio of Functional Monomer to Crosslinking Agent
[0049] Example 3: Evaluation of the adsorption selectivity of the chromium-nickel dual-template molecularly imprinted adsorbent A simulated high-strength steel pickling waste liquid was prepared, in which the contents of iron, chromium, nickel, and copper ions were respectively Fe 3+ 100 mg / L, Cr3+ 75 mg / L, Ni 2+ 65 mg / L, Cu 2+ 50 mg / L, pH adjusted to 3.5 with dilute hydrochloric acid. 0.1 g of the adsorbent prepared in Example 1 was added to 50 mL of a simulated high-strength steel pickling waste solution. The solution was shaken at 25℃ for 4 h to carry out the adsorption reaction. After the reaction, the residual concentrations of various ions in the filtrate were measured. The results are shown in Table 4. The table shows that the material exhibits excellent selective absorption of chromium and nickel, but poor absorption of iron and copper, demonstrating good selective absorption of the material.
[0050] Table 4 Residual Concentration Detection Results
[0051] Example 4: Treatment of mixed acid system waste liquid with chromium-nickel dual-template molecularly imprinted adsorbent The chromium-nickel dual-template molecularly imprinted adsorbent prepared in Example 1 was used to treat sulfuric acid-hydrochloric acid mixed acid pickling waste liquid. The waste liquid composition was: sulfuric acid 3.5%, hydrochloric acid 2.8%, iron 16.2 g / L, chromium 0.58 g / L, and nickel 0.35 g / L.
[0052] (1) Pretreatment and nanofiltration The waste liquid was allowed to settle for 10 hours. The supernatant was filtered through a multi-media filter (25 μm) and a precision filter (8 μm) before entering a primary nanofiltration system (molecular weight cutoff 400 Da, pressure 3.0 MPa) to obtain permeate and concentrate. The permeate then entered a secondary nanofiltration system (molecular weight cutoff 180 Da, pressure 2.0 MPa) to obtain regenerated mixed acid (sulfuric acid 3.2%, hydrochloric acid 2.5%, metal ions <0.1 g / L). The primary acid recovery rate was 88.5%, and the secondary acid recovery rate was 96.2%.
[0053] (2) Adsorption and desorption of primary adsorption column The concentrated solution after nanofiltration in step (1) was adjusted to pH 2.0 and fed into the primary adsorption column at a rate of 4 BV / h. The adsorption column contained 500 g of iron-selective molecularly imprinted adsorbent and was permeated after adsorption at 30°C for 8 hours.
[0054] Desorption was performed using 0.8 mol / L HCl to obtain 560 mL of iron-enriched solution, with an iron recovery rate of 91.8%.
[0055] Take 450 mL of iron enrichment solution and add scrap iron (Fe) 3+ (Fe = 1:0.7), react at 60℃ for 3 h, filter, and then add 30% hydrogen peroxide (Fe... 2+ (0.4 times the molar amount), oxidize at 50℃ for 1.5 h, adjust pH to 2.5, and polymerize at 85℃ for 4 h to obtain polyferric sulfate, in which the total iron content is 11.2%.
[0056] (3) Adsorption and desorption of secondary adsorption column The pH of the first-stage effluent from step (2) was adjusted to 3.5 and fed into the second-stage adsorption column at a rate of 2 BV / h. The adsorption column contained 500 g of the chromium-nickel dual-template molecularly imprinted adsorbent prepared in Example 1 and was saturated at 35°C for 6 h.
[0057] Ni was eluted with 0.2 mol / L HCl 2+ (0.8 BV / h, 2 BV), yielding 310 mL of nickel-rich solution with a recovery rate of 87.6%; Cr was eluted with 1.5 mol / L HCl. 3+ (1.5 BV / h, 3 BV), 270 mL of chromium-enriched solution was obtained, with a recovery rate of 90.3%.
[0058] Mixed calcination: The above nickel and chromium enriched solutions were mixed, the pH was adjusted to 8.5 to precipitate, filtered and washed, and then calcined at 900℃ for 3 h to obtain 16.8 g of chromium-nickel composite oxide, of which the Cr2O3 content was 43.5% and the NiO content was approximately 27.8%. Due to insufficient washing during mixed calcination, undecomposed hydroxides and sodium salts were mixed in. The chromium-nickel composite oxide can be returned to the steelmaking process as a metallurgical raw material.
[0059] Separate calcination: The above nickel enrichment solution was adjusted to pH 8.5 to precipitate, filtered, washed, and then calcined at 900℃ for 3 h to obtain 4.9 g of nickel oxide, of which the NiO content was approximately 98%; the above chromium enrichment solution was adjusted to pH 8.5 to precipitate, filtered, washed, and then calcined at 900℃ for 3 h to obtain 7.4 g of chromium oxide, of which the Cr2O3 content was approximately 98%. The oxide products obtained by separately calcining the two enrichment solutions have higher purity and can be used to prepare high-purity metal salts or electroplating raw materials.
[0060] Example 5: Treatment of hydrochloric acid waste liquid with chromium-nickel dual-template molecularly imprinted adsorbent The chromium-nickel dual-template molecularly imprinted adsorbent prepared in Example 1 was used to treat hydrochloric acid pickling waste liquid. The waste liquid composition was: hydrochloric acid 5.6%, iron 18.5 g / L, chromium 0.72 g / L, and nickel 0.41 g / L. The operation procedure was the same as in Example 4.
[0061] Acid recovery rate: 87.2% for primary nanofiltration, 95.8% for secondary nanofiltration, and 5.1% for regenerated hydrochloric acid. After adsorption and desorption, iron-rich solution, nickel-rich solution, and chromium-rich solution were obtained. These were then processed to obtain polyferric chloride with a total iron content of 11.5%. After mixed calcination, 19.2 g of chromium-nickel composite oxide was obtained.
[0062] Comparative Example 1: Neutralization and Precipitation Method for Treating Mixed Acid Systems Using the same batch of waste liquid from Example 4, lime slurry was added to adjust the pH to 9.0, followed by sedimentation and filtration. Approximately 90 kg of lime was consumed per ton of waste liquid, costing around 200 yuan; approximately 0.3 tons of hazardous sludge were generated, with a disposal cost of around 280 yuan; the total treatment cost was approximately 430 yuan / ton. No product was recovered; iron, chromium, and nickel all entered the sludge. This method only separates metal ions from the pickling waste liquid without any recycling.
[0063] Comparative Example 2: Treatment of Mixed Acid System Waste Liquid by Single-Template Tandem Method Using the same batch of waste liquid from Example 4, after acid recovery, it was sequentially passed through three single-template adsorption columns for iron, chromium, and nickel. Compared with the present invention, this involves one more adsorption column, increasing equipment investment by 40%. Cross-contamination of the enriched solutions also occurred: the chromium enriched solution contained 12.6 g / L of chromium and 2.1 g / L of nickel, with a chromium purity of only 84.3%; the nickel enriched solution contained 8.2 g / L of nickel and 1.9 g / L of chromium, with a nickel purity of only 80.5%. Both results showed a decrease in purity compared to the enriched products treated with the chromium-nickel dual-template molecularly imprinted adsorbent in Example 4. The multiple adsorption columns connected in series increase the land area required, increase raw material input and production process complexity, and raise production costs.
[0064] Table 5 Comparison Results
[0065] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for graded treatment and resource utilization of high-strength steel pickling waste liquid based on chromium-nickel dual-template molecularly imprinted adsorbent, characterized in that, The process flow includes pretreatment of pickling waste liquid, nanofiltration, adsorption and desorption by a primary adsorption column, and adsorption and desorption by a secondary adsorption column. The secondary adsorption column is packed with a chromium-nickel dual-template molecularly imprinted adsorbent, which is a hollow polymer microsphere with a particle size of 50-200 μm, and is prepared by the following method: A dispersant was dissolved in deionized water to prepare an aqueous phase; a template ion solution was prepared by mixing and dissolving chromium and nickel salts in an organic solvent, followed by the addition of 4-vinylpyridine, ethylene glycol dimethacrylate, and azobisisobutyronitrile, along with a porogen, and ultrasonically dispersed to prepare an oil phase; the oil phase was slowly added to the aqueous phase under stirring, and an inert gas was introduced to remove oxygen for 10-20 min, the temperature was raised to 60-80℃, and the polymerization reaction was carried out for 12-24 h; after the reaction, the polymer microspheres were separated, the template ions were eluted, washed, and vacuum dried to obtain the chromium-nickel dual-template molecularly imprinted adsorbent.
2. The method for graded treatment and resource utilization of high-strength steel pickling waste liquid according to claim 1, characterized in that, The dispersant is selected from one or more of polyvinyl alcohol, gelatin or hydroxyethyl cellulose, and the mass fraction of the dispersant is 1% to 5%.
3. The method for graded treatment and resource utilization of high-strength steel pickling waste liquid according to claim 1, characterized in that, The molar ratio of the chromium salt to the nickel salt is 1:2 to 2:
1.
4. The method for graded treatment and resource utilization of high-strength steel pickling waste liquid according to claim 1, characterized in that, The molar ratio of the template ion to 4-vinylpyridine is 1:3 to 1:8; the molar ratio of 4-vinylpyridine to ethylene glycol dimethacrylate is 1:2 to 1:6; and the amount of azobisisobutyronitrile is 1% to 3% of the mass of 4-vinylpyridine.
5. The method for graded treatment and resource utilization of high-strength steel pickling waste liquid according to claim 1, characterized in that, The porogen is toluene or cyclohexane, and the amount used is 20% to 50% of the mass of 4-vinylpyridine.
6. The method for graded treatment and resource utilization of high-strength steel pickling waste liquid according to claim 1, characterized in that, The volume ratio of the oil phase to the water phase is 1:3 to 1:5; the stirring speed is 200 to 800 rpm.
7. The method for graded treatment and resource utilization of high-strength steel pickling waste liquid according to claim 1, characterized in that, Template ions were eluted using a methanol-acetic acid mixed solution with a volume ratio of methanol to acetic acid of 9:1 to 7:3, and the elution time was 24 to 48 hours.
8. The method for graded treatment and resource utilization of high-strength steel pickling waste liquid according to claim 1, characterized in that, The adsorption process of the secondary adsorption column is as follows: the pH of the effluent from the primary adsorption column is adjusted to 3.0~4.0, and the effluent is introduced into the secondary adsorption column at a rate of 1~3 BV / h, and adsorption is carried out at 30~45℃ for 4~8 h until saturation.
9. The method for graded treatment and resource utilization of high-strength steel pickling waste liquid according to claim 1, characterized in that, The desorption process of the secondary adsorption column is as follows: Ni is eluted with 0.1~0.3 mol / L HCl. 2+ The elution rate was 0.5~1.0 BV / h, and the elution volume was 1~3 BV, to obtain a nickel-enriched solution; Cr was eluted with 1.0~2.0 mol / L HCl 3+ The elution rate was 1~2 BV / h, and the elution volume was 2~4 BV, to obtain a chromium-enriched solution.
10. The method for graded treatment and resource utilization of high-strength steel pickling waste liquid according to claim 9, characterized in that, The method for utilizing the nickel-enriched solution and chromium-enriched solution is as follows: adjust the pH of the enriched solution to 8.0-9.0, allow the precipitation reaction to proceed for 1-2 hours, filter and wash, and then calcine at 800-1000℃ for 2-4 hours to obtain nickel oxide and / or chromium oxide.