CN113003793A - Cobalt chloride wastewater cobalt recovery method based on two-stage resin separation - Google Patents
Cobalt chloride wastewater cobalt recovery method based on two-stage resin separation Download PDFInfo
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- 239000010941 cobalt Substances 0.000 title claims abstract description 42
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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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Environmental & Geological Engineering (AREA)
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- Treatment Of Water By Ion Exchange (AREA)
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Abstract
The invention discloses a method for recovering cobalt in cobalt chloride wastewater based on two-stage resin separation, and belongs to the technical field of water treatment. The invention removes organic matters and metal impurities in the cobalt chloride wastewater by a two-stage resin adsorption process, thereby achieving the purpose of deeply purifying the cobalt chloride solution. The method comprises the following specific steps: (1) filtering the wastewater by a filtering device to remove fine particles and colloidal substances; (2) introducing the effluent obtained in the step (1) into a primary resin adsorption tower to remove organic matters in the wastewater; (3) introducing the effluent of the primary resin in the step (2) into a secondary resin adsorption tower to remove metal ions in the wastewater; (4) and (3) performing regeneration treatment after the resin is adsorbed and saturated in the steps (2) and (3). The invention realizes the continuous and recycling treatment of the cobalt chloride solution and the desorption solution, reduces the treatment cost and strengthens the treatment effect by utilizing the water power.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a method for recovering cobalt in cobalt chloride wastewater based on two-stage resin separation.
Background
Cobalt is an important strategic mineral resource, has the characteristics of high temperature resistance, corrosion resistance, high strength, high magnetism and the like, is widely applied to the industries of aerospace, mechanical manufacturing, electrical appliances, magnetic materials, ceramics and the like, and has important significance on national economy and social development. Cobalt chloride, a cobalt-containing compound, is also widely used in the industries of instrument manufacture, ceramics, paints, livestock husbandry, brewing, national defense, and the like. Cobalt is produced mostly as a companion metal due to its inherent iron-philic and sulfur-philic duality. Currently, industrial cobalt is mainly recovered to obtain byproducts in processing of copper, nickel, iron and other mineral products or is prepared by hydrometallurgical intermediate products, and the obtained crude cobalt product contains metal impurities in various ion forms, such as copper (Cu), iron (Fe), zinc (Zn), cadmium (Cd) and the like, and needs to be further purified.
Among them, cadmium (Cd) is a metal element harmful to the human body, which causes irritation to the respiratory tract of the human body, damages the kidney of the human body, and also causes osteoporosis and malacia. Cadmium is present in the cobalt solution and adversely affects the ductility of subsequent cobalt-based materials, so it is necessary to remove cadmium deeply from the cobalt solution to ensure the reliability of the cobalt-based materials in practical use. Most methods for removing cadmium from a cobalt solution are alkalization or sulfuration precipitation, reduction replacement, extraction and ion exchange. Wherein, the amount of reagent consumed by the precipitation method is too large, and when the concentration of Cd is too low, the Cd can not be completely removed, and the loss of main metal Co is also large; a large amount of cobalt powder is consumed for reduction and replacement, and the operation cost is overhigh; the extraction method needs multi-stage extraction to deeply remove impurities, is complex to operate and is easy to mix organic phases in a solution; the ion exchange method has obvious effect of separating and removing cobalt and cadmium in a chloride system because cobalt and cadmium have morphological difference in a chloride ion-containing solution in an acid system, and anion exchange resin is selected for adsorbing and removing CdCl5 3-。
If the cobalt solution contains substances such as an extractant, kerosene and the like, the subsequent deep purification treatment of the cobalt solution is adversely affected, and meanwhile, the cobalt-based material surface is also subjected to 'dark spots'. The traditional oil removing method adopts activated carbon for adsorption, but the adsorption capacity of the activated carbon in an aqueous solution system is limited, and the activated carbon after saturated adsorption belongs to dangerous solid waste and needs special treatment. And a macroporous nonpolar special adsorption resin is selected to deeply remove organic matters in the cobalt solution, so that the process is simple, the residue-free impurity removal can be realized, and meanwhile, the effective desorption and the cyclic regeneration utilization of the resin can be realized by selecting a proper desorption agent.
Therefore, in order to solve the technical problem of recovering cobalt from a cobalt chloride solution containing organic substances and metal impurities, the cobalt chloride solution can be efficiently treated in a green and economical manner by a resin method.
Disclosure of Invention
Problems to be solved
The invention provides a method for continuously treating organic matters and metal impurities (cadmium) in a cobalt chloride solution, aiming at the technical problem of removing the metal impurities (cadmium) and recovering cobalt in the existing cobalt chloride system containing the organic matters. The invention separates organic matters and metal impurities (cadmium) in the wastewater by the effective combination of two-stage resin adsorption to achieve the aim of recovering cobalt, the whole treatment process has no secondary pollution, continuous treatment can be realized, desorption liquid of two-stage resin can be recycled, and the treatment cost is reduced.
Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a method for recovering cobalt in cobalt chloride wastewater based on two-stage resin separation, which comprises the following steps:
(1) filtering the wastewater by a filtering device to remove fine particles and colloidal substances;
(2) introducing the effluent obtained in the step (1) into a primary resin adsorption tower to remove organic matters in the wastewater;
(3) introducing the effluent of the primary resin in the step (2) into a secondary resin adsorption tower to remove metal ions in the wastewater;
(4) and (3) performing regeneration treatment after the resin is adsorbed and saturated in the steps (2) and (3). And (3) blowing off the primary resin in the step (2) by using water vapor at the temperature of 120-150 ℃ and the pressure of 0.15-0.6 Mpa to obtain regenerated primary resin and a primary desorption solution after condensation of the steam. And (3) enabling the primary desorption liquid to sequentially flow through a heat exchanger and an oil-water separator, recovering the upper-layer oil, and taking the lower-layer water as a secondary resin desorption agent in the step (3).
Preferably, in the step (1), the precision of the filtering device is less than 10 μm and the filtering device is corrosion-resistant.
Preferably, both steps (2) and (3) are carried out in a countercurrent mode. In the step (2), the flow speed V1 of the wastewater adsorbed by the primary resin is 1-4 BV/h; in the step (3), the flow speed V2 of the wastewater adsorbed by the secondary resin is 3-6 BV/h.
Preferably, in the step (2), a macroporous nonpolar special adsorption resin is selected for removing the organic matters, and the specific surface area and the particle size of the macroporous special adsorption resin are respectively 1100-1400 m2The thickness is between 0.4 and 1.25 mm, and the chemical framework is one or two of polystyrene and polyacrylate; in the step (3), a strong base anion exchange resin is selected for removing metal ion impurities, and the exchange capacity and the specific surface area of the strong base anion exchange resin are respectively 1.0-8.0 mmol/g and 0.1-50 m2Between the/g, the chemical skeleton is one or two of polystyrene and polyacrylate.
Preferably, when the organic matter content in the wastewater is too high (TOC is more than 300 mg/L), the effluent water in the step (2) is refluxed to the water inlet end of the step (2) at the reflux ratio of 5% -100%, and the step (2) is repeated.
Preferably, in the step (4), after the primary resin is desorbed by downstream blowing of water vapor for 4-6 batches, 1.5-3 BV of 6% -10% alkali liquor is used at a flow rate of 1-2 BV/h to strengthen desorption for one batch, so as to ensure the stable adsorption effect of the resin; and after the water on the lower layer is desorbed, carrying out resin transformation by using 1-2 BV of 4% -6% HCl.
Preferably, in the step (4), the usage amount of the desorption agent is 2-8 BV, the flow rate of the desorption agent is 1-3 BV/h, and the desorption agent is one or more of water vapor, liquid caustic soda and dilute hydrochloric acid.
Preferably, after the step (3), refluxing the effluent to the water inlet end of the step (2) in a ratio of 20-100%, and repeating the step (2).
Advantageous effects
Compared with the prior known technology, the invention has the following remarkable effects:
(1) the invention relates to a recovery method of cobalt chloride waste water cobalt based on two-stage resin separation, which adopts two-stage different resins to treat organic matters and metal impurities in waste water, wherein macroporous non-polar special adsorption resin is preferentially selected to remove the organic matters in the waste water, and effluent water of a first-stage resin is controlled to flow back to a water inlet end of the resin for re-adsorption so as to ensure that the content of the organic matters does not influence the adsorption quantity of the second-stage resin for removing the metal impurities;
(2) according to the recovery method of cobalt chloride wastewater cobalt based on two-stage resin separation, the metal impurities (cadmium) removed by the second-stage resin are strong-base anion exchange resin, so that the cobalt content in the solution can not be reduced while cadmium is removed;
(3) according to the recovery method of cobalt chloride wastewater cobalt based on two-stage resin separation, the wastewater is adsorbed in a countercurrent adsorption mode, so that the hydraulic retention time of the wastewater in a resin column is prolonged, and the wastewater treatment efficiency is improved; desorption is performed in a concurrent flow mode, so that the pollution of the upper resin is reduced, and the service life of the resin is prolonged;
(4) according to the recovery method of cobalt chloride wastewater cobalt based on two-stage resin separation, when the two-stage resin is desorbed and regenerated, the first-stage resin is blown off by steam, then the desorption liquid is subjected to oil-water separation, and the lower layer water is used as the second-stage resin desorption agent.
Drawings
FIG. 1 is a schematic flow diagram of a method for recovering cobalt from cobalt chloride wastewater based on two-stage resin separation.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
The cobalt chloride wastewater of this example was wastewater from cobalt chloride production from a company of Tanzhou, with a TOC of about 202 mg/L, Cd at a concentration of 1.9 mg/L, Co at a concentration of 1.6X 105mg/L and the pH value of the solution is 4.5, and the treatment steps aiming at the waste water are as follows:
(1) and (3) filtering: wastewater with a particle size of 4m3The flow rate of the water per hour is passed through a bag filter to remove suspended matters in the wastewater.
(2) First-stage resin adsorption: and (3) feeding the filtered wastewater into the lower end of an adsorption device filled with macroporous nonpolar special adsorption resin, and performing countercurrent adsorption to remove organic matters in the wastewater. The ratio of height to diameter of the filled macroporous nonpolar special adsorption resin is 3: 1, adsorbing 50BV of wastewater at the flow rate of 3.5BV/h, and reducing the TOC of resin effluent to 26.79 mg/L.
(3) Secondary resin adsorption: and (3) sending the effluent of the primary resin into a secondary adsorption device, and carrying out countercurrent adsorption to remove the metal cadmium in the wastewater. D201 anion exchange resin is filled in the secondary adsorption device, and the height-diameter ratio is 3: 1, the adsorption flow rate is 3.5BV/h, the adsorption capacity is 280BV, the concentration of Cd in the resin effluent is 0.36mg/L, and the requirement of customers on cobalt recovery is met (Cd is less than 0.5 mg/L).
(4) When the two-stage resin is saturated in adsorption, the two-stage resin needs to be regenerated, and the method is specifically operated as follows:
firstly, introducing 130 ℃ water vapor into the top end of a primary resin adsorption device, closing a bottom valve, adjusting the angle of the bottom valve when the pressure in the device reaches 0.25Mpa, and blowing off the water vapor for 2 hours under the premise of ensuring that the pressure in the device is basically stabilized at 0.25Mpa to obtain 2 BV condensate; and then the condensate flows through the heat exchange device at the flow velocity of 0.5m/s, the temperature of the condensate is reduced to be below 50 ℃, the condensate enters an oil-water separator, oil-water separation of the condensate is realized, and lower-layer water used for a secondary resin desorption agent is obtained.
And (3) enabling the treated condensate water to flow into a secondary resin device, circulating a desorption agent in the device for 2 hours at the flow rate of 1BV/h through a circulating pump, and after the circulation is finished, enabling the condensate water to flow out of the adsorption device at the flow rate of 1 BV/h. The usage amount of the desorption agent in the secondary resin desorption process is 5BV, and when the amount of the condensed water is insufficient, part of the desorption agent needs to be added externally. After the desorption is finished, 1BV 4 percent HCl flows through the adsorption device at the flow rate of 1BV/h to realize resin transformation, and finally 2 BV soft water is used for cleaning the residual diluted acid in the resin, and the soft water is reused in the next batch of resin desorption agent.
The desorption rate of the first-stage resin can reach 93 percent after the first-stage resin is subjected to steam stripping, so that 2 BV 7 percent liquid caustic soda needs to be used for strengthening regeneration once after 5 batches of desorption; after the second-level resin is desorbed by 5BV of soft water, the desorption rate can basically reach 100 percent.
Example 2
The cobalt chloride wastewater of this example is wastewater from cobalt chloride production from Tianjin, a new energy materials company, and the TOC of the wastewater is about 147 mg/L, Cd, 2.316 mg/L, Co, and 1.95 × 105mg/L and the pH value of the solution is 3.9, and the treatment steps aiming at the waste water are as follows:
(1) and (3) filtering: wastewater with a particle size of 5m3The flow rate of the water per hour is passed through a bag filter to remove suspended matters in the wastewater.
(2) First-stage resin adsorption: and (3) feeding the filtered wastewater into the lower end of an adsorption device filled with macroporous nonpolar special adsorption resin, and performing countercurrent adsorption to remove organic matters in the wastewater. The ratio of height to diameter of the filled macroporous nonpolar special adsorption resin is 3: 1, adsorbing 65 BV of wastewater at the flow rate of 4 BV/h, and reducing the TOC of resin effluent to 9.4 mg/L.
(3) Secondary resin adsorption: and (3) sending the effluent of the primary resin into a secondary adsorption device, and carrying out countercurrent adsorption to remove the metal cadmium in the wastewater. D201 anion exchange resin is filled in the secondary adsorption device, and the height-diameter ratio is 3.5: 1, the adsorption flow rate is 3 BV/h, the adsorption capacity is 300 BV, the concentration of Cd in the resin effluent is 0.62 mg/L, and the requirement of a client on the recovery of Cd in the cobalt solution is met (Cd is less than 0.7 mg/L).
(4) When the two-stage resin is saturated, the two-stage resin needs to be regenerated, the operation steps are basically the same as the desorption step in the embodiment 1, except that the pressure in the device is 0.3Mpa when the one-stage resin is desorbed; the desorption dosage of the secondary resin is 7 BV.
Example 3
The wastewater in this example is cobalt chloride wastewater from the superfine powder material producing company in Hubei, the TOC of the wastewater is about 317 mg/L, Cd, 1.739 mg/L, Co, and 2.01 × 105mg/L, pH 4.8, and the treatment steps aiming at the waste water are as follows:
(1) and (3) filtering: wastewater with a particle size of 5m3The flow rate of the water per hour is passed through a bag filter to remove suspended matters in the wastewater.
(2) First-stage resin adsorption: and (3) feeding the filtered wastewater into the lower end of an adsorption device filled with macroporous nonpolar special adsorption resin, and performing countercurrent adsorption to remove organic matters in the wastewater. The ratio of height to diameter of the filled macroporous nonpolar special adsorption resin is 3.5: 1, adsorbing 45 BV of wastewater at the flow rate of 3 BV/h, reducing the TOC of resin effluent to 43.7 mg/L, refluxing 80% of first-stage resin effluent to a water inlet end, and repeating first-stage adsorption, wherein the TOC of the resin effluent is 36.2 mg/L.
(3) Secondary resin adsorption: and (3) sending the first-stage resin backflow effluent into a second-stage adsorption device, and removing the metal cadmium in the wastewater through countercurrent adsorption. D201 anion exchange resin is filled in the secondary adsorption device, and the height-diameter ratio is 3: 1, the adsorption flow rate is 4 BV/h, the adsorption capacity is 300 BV, the concentration of Cd in the resin effluent is 0.47 mg/L, and the requirement of a client on the recovery of Cd in the cobalt solution is met (Cd is less than 0.5 mg/L).
(4) When the two-stage resin is saturated, the two-stage resin needs to be regenerated, and the operation steps are the same as the desorption step in the example 1.
By the treatment method for recovering cobalt from cobalt chloride wastewater, organic matters and metal impurities in the waste liquid can be separated simultaneously, and the two resins have high adsorption stability and can be repeatedly regenerated and used for many times; in the desorption process, continuous operation and internal recycling of desorption liquid can be realized, and the wastewater treatment cost is reduced.
It should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and are not limitative, and that modifications may be made as appropriate without departing from the scope of the present invention as defined by the appended claims. The embodiments of the present invention are shown in the drawings, and the practical use process and the removal of metal impurities are not limited thereto, and if similar technical schemes and examples without inventive step are present, they will fall within the scope of the present invention described herein.
Claims (8)
1. A method for recovering cobalt in cobalt chloride wastewater based on two-stage resin separation is characterized by comprising the following specific steps:
(1) filtering the wastewater by a filtering device to remove fine particles and colloidal substances;
(2) introducing the effluent obtained in the step (1) into a primary resin adsorption tower to remove organic matters in the wastewater;
(3) introducing the effluent of the primary resin in the step (2) into a secondary resin adsorption tower to remove metal ions in the wastewater;
(4) performing regeneration treatment after the resin in the steps (2) and (3) is adsorbed and saturated;
wherein, the first-stage resin in the step (2) is blown off by water vapor with the temperature of 120-150 ℃ and the pressure of 0.15-0.6 Mpa to obtain regenerated first-stage resin and first-stage desorption liquid after condensation of the vapor;
and (3) enabling the primary desorption liquid to sequentially flow through a heat exchanger and an oil-water separator, recovering the upper-layer oil, and taking the lower-layer water as a secondary resin desorption agent in the step (3).
2. The recovery method of cobalt in cobalt chloride wastewater based on two-stage resin separation as claimed in claim 1, characterized in that: in the step (1), the precision of the filtering device is less than 10 mu m, and the filtering device is corrosion-resistant.
3. The recovery method of cobalt in cobalt chloride wastewater based on two-stage resin separation as claimed in claim 1, characterized in that: both the step (2) and the step (3) adopt a countercurrent mode for adsorption;
in the step (2), the flow speed V1 of the wastewater adsorbed by the primary resin is 1-4 BV/h; in the step (3), the flow speed V2 of the wastewater adsorbed by the secondary resin is 3-6 BV/h.
4. The method for recovering cobalt in cobalt chloride wastewater based on two-stage resin separation as claimed in claim 1, characterized in that: in the step (2), a macroporous nonpolar special adsorption resin with specific surface area and particle size of 1100-1400 m is selected for removing organic matters2The thickness is between 0.4 and 1.25 mm, and the chemical framework is one or two of polystyrene and polyacrylate; in the step (3), a strong base anion exchange resin is selected for removing metal ion impurities, and the exchange capacity and the specific surface area of the strong base anion exchange resin are respectively 1.0-8.0 mmol/g and 0.1-50 m2Between the/g, the chemical skeleton is one or two of polystyrene and polyacrylate.
5. The recovery method of cobalt in cobalt chloride wastewater based on two-stage resin separation as claimed in claim 1, characterized in that: and (3) when the organic matter content in the wastewater is too high (TOC is more than 300 mg/L), refluxing the effluent water in the step (2) to the water inlet end of the step (2) at a reflux ratio of 5-100%, and repeating the step (2).
6. The recovery method of cobalt in cobalt chloride wastewater based on two-stage resin separation as claimed in claim 1, characterized in that: in the step (4), after the primary resin is desorbed by downstream blowing of water vapor for 4-6 batches, 1.5-3 BV of 6% -10% alkali liquor is used for reinforcing desorption for one batch at the flow rate of 1-2 BV/h so as to ensure the stable adsorption effect of the resin; and after the water on the lower layer is desorbed, carrying out resin transformation by using 1-2 BV of 4% -6% HCl.
7. The recovery method of cobalt in cobalt chloride wastewater based on two-stage resin separation as claimed in claim 1, characterized in that: in the step (4), the dosage of the desorption agent is 2-8 BV, the flow rate of the desorption agent is 1-3 BV/h, and the desorption agent is one or more of water vapor, liquid caustic soda and dilute hydrochloric acid.
8. The recovery method of cobalt in cobalt chloride wastewater based on two-stage resin separation as claimed in claim 1, characterized in that: and (4) after the step (3), refluxing the effluent to the water inlet end of the step (2) in a ratio of 20-100%, and repeating the step (2).
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