CN107176711B - Process for efficiently recovering copper in high-concentration berberine wastewater - Google Patents
Process for efficiently recovering copper in high-concentration berberine wastewater Download PDFInfo
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- CN107176711B CN107176711B CN201710261161.XA CN201710261161A CN107176711B CN 107176711 B CN107176711 B CN 107176711B CN 201710261161 A CN201710261161 A CN 201710261161A CN 107176711 B CN107176711 B CN 107176711B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
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- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C02F1/705—Reduction by metals
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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Abstract
The invention belongs to the field of water treatment application and resource utilization, and relates to a process for efficiently recovering copper in high-concentration berberine waste water. The process comprises the steps of adding berberine copper-containing wastewater into a water treatment flocculant and a Polyacrylamide (PAM) mixed reagent, and intensively stirring at 1000-; adding NaOH, and adjusting the pH value of the wastewater to 2-3.5; the precipitate and suspended matter are then removed by filtration and centrifugation. After the obtained wastewater is heated, iron powder is slowly added. After the reaction is finished, filtering to obtain copper simple substance precipitate, and allowing effluent to enter a secondary reaction; reacting for 20-30min, filtering and precipitating, and discharging the supernatant reaching the standard. The process has the advantages of simple operation, stable operation, low cost, high purity of the recovered copper simple substance, good economic benefit and good application prospect.
Description
Technical Field
The invention belongs to the field of water treatment application and resource utilization, and relates to a simple and efficient process for recovering copper in high-concentration copper-containing berberine wastewater by a flocculation and iron reduction method.
Background
The berberine copper-containing wastewater is mainly derived from a copper removal process link in berberine generation, is a mixture of waste liquid of copper removal reaction and berberine crude product cleaning liquid, and mainly comprises berberine, copper ions and reaction intermediate products. The berberine copper-containing wastewater is typical chemical synthesis pharmaceutical wastewater, and is dark green solution, so that the berberine copper-containing wastewater has strong acidic pungent taste, the pH value is about 1, the concentration of organic matters is as high as tens of thousands to hundreds of thousands of mg/L, and the average value of the content of copper chloride in the wastewater is 1.5-2 ten thousands of mg/L. Because the concentration of copper ions in the wastewater is high, the wastewater is discharged to a sewage treatment plant without pretreatment, and huge impact is brought to the biological treatment process of the subsequent sewage treatment plant. Meanwhile, the waste water has higher content of copper ions, so the waste water has higher recycling value.
Therefore, the copper in the berberine copper-containing wastewater is recovered, so that resource utilization can be realized on one hand, and the difficulty in subsequent wastewater treatment can be reduced on the other hand. At present, in order to recover copper ions in berberine production wastewater, an invention patent (Zengnung et al, ZL201310042379.8) discloses a process for preparing basic copper chloride by utilizing berberine copper-containing wastewater, and 99.9% of copper in the wastewater can be recovered. However, the copper chloride hydroxide recovered by the method needs to be further treated, and berberine and acid in water need to be further treated, so that the process is more complicated; shokkniu et al used electrochemical bipolar method to treat high concentration copper-containing berberine pharmaceutical wastewater (environmental engineering Proc., 2011, 1 (4): 295-. However, in practical application of the method, electrodes are easy to scale, further reaction is affected, and production cannot be carried out. The preparation method comprises the steps of adopting an iron-carbon micro-electrolysis cell-ion exchange column combined process to recover copper from berberine pharmaceutical wastewater in the case of Zuixiayu and the like, wherein the removal rate of copper ions reaches about 97%, the removal rate of organic matter concentration reaches over 44%, and 13kg of copper can be recovered from each ton of wastewater (according to the technical report of environmental engineering, 2012,2 (4): 319-. However, the method for treating copper-containing berberine wastewater cannot be effectively operated for a long time in practical engineering, because the wastewater contains colloidal substances, when the pH value in the wastewater is adjusted to be more than 3, the colloidal substances are changed into solid state from a dissolved state, and the reaction process of reducing copper ions into elemental copper is influenced, so that the reaction is insufficient; on the other hand, the separated jelly is adhered to the wall of the reactor, and the blockage of a wastewater conveying pipeline is easily caused, so that the subsequent treatment of the wastewater is influenced.
Based on the problem that jelly in the actual recovery process of copper-containing wastewater affects the reaction process and the reaction efficiency, the method firstly removes the jelly organic matters by flocculation and then carries out copper recovery on the berberine copper-containing wastewater by a process of replacing copper ions by a secondary iron simple substance. In the existing reports, a process for recovering the berberine copper-containing wastewater by combining flocculation and secondary iron reduction is not available.
Disclosure of Invention
The invention provides a process for efficiently recovering copper in high-concentration berberine waste water, which has the advantages of simple operation, stable operation, low cost, high purity of recovered copper simple substance, good economic benefit and good application prospect.
The invention relates to a process for efficiently recovering copper in high-concentration berberine waste water, which adopts the following technical scheme:
(1) uniformly mixing the berberine copper-containing wastewater in a production period, and adding a water treatment flocculant and a Polyacrylamide (PAM) mixed reagent according to the COD concentration, wherein the water treatment flocculant comprises aluminum sulfate, aluminum chloride, ferric sulfate, ferric chloride, polymeric ferric sulfate, polymeric aluminum chloride, polymeric aluminum ferric chloride and other flocculants; stirring strongly at 1000-;
(2) adding NaOH, fully stirring and uniformly mixing, adjusting the pH value of the wastewater to 2-3.5, and standing for 30 min;
(3) and (4) carrying out centrifugal separation on the wastewater by adopting a filter type centrifugal machine, wherein the rotating speed is 3000-5000r/min, and the centrifugal time is 10-25min, so as to remove precipitates and suspended matters. The supernatant fluid after centrifugal separation enters a first-stage iron reduction reaction;
(4) heating the wastewater to 75-95 ℃; then according to Cu in the wastewater2+According to the concentration of the iron powder required by the reduction reaction, adding 10-40% of excessive iron powder in a slowly distributed manner. When the iron powder is added, the wastewater is continuously stirred, so that the iron powder and the wastewater are fully contacted. Adding all iron powder, continuously stirring and reacting at 80-95 ℃ for 20-50min, after the reaction is finished, filtering to obtain copper simple substance precipitate, and allowing the effluent to enter a secondary reaction; (2) and (3) adding 10-20% of the total amount of iron added in the first-stage reaction into the effluent after the first-stage reduction reaction at the temperature of 80-95 ℃, carrying out a second-stage reaction for 20-30min, filtering and precipitating, and discharging the supernatant reaching the standard.
The method takes high-concentration copper-containing berberine production wastewater as a treatment object, mainly adopts a flocculating agent to remove colloidal organic matters in the wastewater, then adopts cheap iron powder as a raw material, and reduces Cu in the wastewater through simple iron reduction2+The copper simple substance can be used for recovering and recycling the metal copper resource, and simultaneously can also remove colloidal organic matters in the wastewater and reduce COD in the wastewaterIn time, the blockage of the colloidal organic matters in the wastewater in the actual operation of a factory to the pipeline is reduced. The method can recover more than 99% of copper in the wastewater and Cu in the effluent2+The concentration is lower than 50mg/L, and the biodegradability of the wastewater is effectively improved.
Drawings
FIG. 1 is a process flow chart for efficiently recovering copper from high-concentration berberine waste water.
Detailed Description
Example 1 400mL of copper-containing berberine containing wastewater, Cu2+The concentration is 18000 mg/L, CODCrThe concentration was 87000mg/L, the initial pH was 0.1. Adding 10g of basic aluminum chloride, stirring for 20 minutes at the rotating speed of 2000r/min, then adding 0.4g of PAM coagulant aid, stirring for 10 minutes at the rotating speed of 1000r/min, then adding 5g of NaOH to adjust the pH value of the wastewater to 3.0, and standing for reaction for 30 minutes. Centrifuging at the rotating speed of 4000r/min for 20min, and collecting 320mL of supernatant waste liquid for primary reduction reaction. Heating the wastewater to 90 ℃, slowly adding 6.6g of iron powder with the purity of more than 95%, and continuously stirring and reacting for 30min at 500 r/min. Then, water is discharged and filtered to obtain elemental copper after the first-stage reaction, and the wastewater is subjected to a second-stage reduction reaction. First-order reaction effluent Cu2+The concentration was 53 mg/L. Before the second-stage reaction, heating the wastewater to 90 ℃, slowly adding 0.66g of iron powder with the purity of more than 95%, continuously stirring at 500r/min for reaction for 30min, discharging water, filtering to obtain a mixture of copper, iron and the like after the second-stage reaction, and discharging Cu in the water2+The concentration was 8.9mg/L and the CODCr concentration was 53000 mg/L.
Example 2400 mL of copper-containing berberine generating wastewater, Cu2+The concentration is 18000 mg/L, CODCrThe concentration was 87000mg/L, the initial pH was 0.1. Adding 8g of basic aluminum chloride, stirring for 30 minutes at the rotating speed of 3000r/min, then adding 0.2g of PAM coagulant aid, stirring for 10 minutes at the rotating speed of 500r/min, then adding 5.2g of NaOH to adjust the pH value of the wastewater to 3.5, and standing for reaction for 40 minutes. Centrifuging at the rotating speed of 5000r/min for 20min, and collecting 320mL of supernatant waste liquid for primary reduction reaction. Heating the wastewater to 75 ℃, slowly adding 5.1g of iron powder with the purity of more than 95%, and continuously stirring and reacting for 30min at 1000 r/min. Then water is discharged and filtered to obtain the first-stage reactionThe simple substance copper and the waste water are sent to a secondary reduction reaction tank. Cu in first-stage effluent2+The concentration was 131 mg/L. Maintaining the temperature of the second-stage reaction at 90 deg.C, slowly adding 0.51g of iron powder with purity of above 95%, stirring and reacting for 30min at 500r/min, discharging water, filtering to obtain mixture of copper and iron after the second-stage reaction, and discharging Cu from the second-stage water2+The concentration was 29mg/L and the CODCr concentration was 67000 mg/L.
Example 3400 mL of copper-containing Berberine production wastewater, Cu2+The concentration is 18000 mg/L, CODCrThe concentration was 87000mg/L, the initial pH was 0.1. Adding 10g of basic aluminum chloride, stirring for 30 minutes at the rotating speed of 3000r/min, then adding 0.4g of PAM coagulant aid, stirring for 10 minutes at the rotating speed of 500r/min, then adding 4.6g of NaOH to adjust the pH value of the wastewater to 2.5, and standing for reaction for 30 minutes. Centrifuging for 30min at the rotating speed of 5000r/min, and collecting 320mL of supernatant waste liquid for primary reduction reaction. Heating the wastewater to 90 ℃, slowly adding 6.6g of iron powder with the purity of more than 95%, and continuously stirring and reacting for 40min at 1000 r/min. And then discharging water, filtering to obtain elementary copper after the first-stage reaction, and conveying the wastewater to a second-stage reduction reaction tank. Cu in first-stage effluent2+The concentration was 461 mg/L. Maintaining the temperature of the second-stage reaction at 90 deg.C, slowly adding 1.11g of iron powder with purity of above 95%, stirring and reacting for 40min at 500r/min, discharging water, filtering to obtain mixture of copper and iron, etc., and discharging Cu from the second-stage reaction water2+The concentration was 46mg/L and the CODCr concentration was 67000 mg/L.
Claims (1)
1. A process for efficiently recovering copper in high-concentration berberine waste water is characterized by comprising the following steps,
(1) uniformly mixing the berberine copper-containing wastewater in a production period, and adding a water treatment flocculant and a Polyacrylamide (PAM) mixed reagent according to the COD concentration, wherein the water treatment flocculant comprises aluminum sulfate, aluminum chloride, ferric sulfate, ferric chloride, polymeric ferric sulfate, polymeric aluminum chloride and polymeric aluminum ferric chloride flocculant; stirring strongly at 1000-;
(2) adding NaOH, fully stirring and uniformly mixing, adjusting the pH value of the wastewater to 2-3.5, and standing for 30 min;
(3) centrifuging the wastewater by adopting a filter centrifuge at the rotating speed of 3000-;
(4) heating the wastewater to 75-95 ℃; then according to Cu in the wastewater2+According to the concentration, adding 10-40% excessive iron powder slowly in a distributed manner according to the amount of the iron powder required by the reduction reaction; when adding iron powder, continuously stirring the wastewater to ensure that the iron powder is fully contacted with the wastewater; adding all iron powder, continuously stirring and reacting at 80-95 ℃ for 20-50min, after the reaction is finished, filtering to obtain copper simple substance precipitate, and allowing the effluent to enter a secondary reaction;
(5) and (3) adding 10-20% of the total amount of iron added in the first-stage reaction into the effluent after the first-stage reduction reaction at the temperature of 80-95 ℃, carrying out a second-stage reaction for 20-30min, filtering and precipitating, and discharging the supernatant reaching the standard.
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