CN111994988B - Method for extracting and separating heavy metals in pickling waste liquid - Google Patents

Method for extracting and separating heavy metals in pickling waste liquid Download PDF

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CN111994988B
CN111994988B CN202010688965.XA CN202010688965A CN111994988B CN 111994988 B CN111994988 B CN 111994988B CN 202010688965 A CN202010688965 A CN 202010688965A CN 111994988 B CN111994988 B CN 111994988B
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waste liquid
pickling waste
heavy metals
extracting
precipitator
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CN111994988A (en
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薛剑锋
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Jiangmen Taihui Environmental Protection Technology Co ltd
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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
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • 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
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C22B3/409—Mixtures at least one compound being an organo-metallic compound
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for extracting and separating heavy metals in pickling waste liquid, which comprises the following steps: adding an organic extractant into the pickling waste liquid for extraction to obtain an extraction liquid containing heavy metal ions; adding a precipitator into the extract liquor to precipitate heavy metals, and separating precipitates; the organic extractant comprises the following components in percentage by weight: 10-20% of 2-ethylhexyl phosphate mono-2-ethylhexyl ester, 10-20% of tributyl phosphate, 1-10% of polyaspartic acid and the balance of diluent. The invention firstly utilizes the organic extractant with higher extraction rate to extract the heavy metal in the pickling waste liquid, achieves the aim of removing the heavy metal in the pickling waste liquid, reduces the amount of the heavy metal-containing waste liquid, and then utilizes the precipitator to precipitate and separate out the heavy metal ions in the extraction liquid, thereby reducing the dosage of the precipitator and realizing the recycling of the extractant. The method can effectively remove heavy metals in the pickling waste liquid, and has the advantages of simple treatment process, low cost, environmental protection and no pollution.

Description

Method for extracting and separating heavy metals in pickling waste liquid
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a method for extracting and separating heavy metals in pickling waste liquid.
Background
The pickling waste liquid is waste water generated when acid pickling treatment is performed by using acids such as sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid and the like in order to remove oxides on metal surfaces, and is mostly from steel plants or electroplating plants. The pickling waste liquid contains a large amount of ferrous iron or ferric ions, free acid and a small amount of heavy metals such as chromium, nickel and the like, has strong corrosivity, and if the pickling waste liquid is directly discharged, a sewer and a polluted water body are corroded, and the heavy metals contained in the pickling waste liquid can threaten the health of human beings by the enrichment of a food chain.
The prior art has various methods for treating the pickling waste liquid, including a precipitation method, an electrolysis method, an ion exchange method and the like, which play a positive role in treating the pickling waste liquid to a certain extent, but have higher treatment cost, complex treatment process and lower removal rate of heavy metal ions in the waste liquid.
Therefore, a more effective method for removing heavy metals from the pickling waste liquid is needed.
Disclosure of Invention
Based on the above, in order to solve the defects and shortcomings of the prior art, the invention aims to provide a method for extracting and separating heavy metals from pickle liquor.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a method for extracting and separating heavy metals in pickle liquor comprises the following steps: adding an organic extractant into the pickling waste liquid for extraction to obtain an extraction liquid containing heavy metal ions; adding a precipitator into the extract liquor to precipitate heavy metals, and separating precipitates; the organic extractant comprises the following components in percentage by weight: 10-20% of 2-ethylhexyl phosphate mono-2-ethylhexyl ester, 10-20% of tributyl phosphate, 1-10% of polyaspartic acid and the balance of diluent.
2-ethylhexyl phosphate mono-2-ethylhexyl ester and tributyl phosphate may be bonded to the metal ion. Polyaspartic Acid (PASP) is one kind of polyamino acid, has biodegradability and good chelating property for metal ions. The inventor discovers through experimental study that: when the 2-ethylhexyl phosphate mono-2-ethylhexyl ester, the tributyl phosphate and the polyaspartic acid are used independently, the separation effect on the chromium and the nickel is poor. When the 2-ethylhexyl phosphate mono-2-ethylhexyl ester, the tributyl phosphate and the polyaspartic acid are compounded and used according to the proportion provided by the invention, the synergistic effect is achieved, the high selectivity is achieved on heavy metal ions such as chromium and nickel in the pickling waste liquid, the heavy metals can be effectively extracted and separated from the pickling waste liquid, and the extraction rate of chromium and nickel is high.
In the present invention, chromium means trivalent chromium ions and nickel means divalent nickel ions unless otherwise specified.
Preferably, the diluent is sulfonated kerosene.
Preferably, the organic extractant consists of the following components in percentage by weight: 15% of 2-ethylhexyl phosphate, 15% of tributyl phosphate, 5% of polyaspartic acid and the balance of a diluent. When the organic extractant consists of the components, the extraction rate of chromium and nickel is highest.
Preferably, the volume ratio of the organic extractant to the pickling waste liquid is 1 (4-6). The organic extractant is added according to the proportion for extraction, so that the heavy metal ions in the pickling waste liquid can be extracted more thoroughly.
Preferably, the precipitant is a YQ-0002 precipitant and/or a DTC precipitant. The two precipitants have better capturing and precipitating effects on heavy metal ions, and the inventor finds out through experiments that the two precipitants are prepared from YQ-0002 precipitant: when the DTC precipitator (2-4) is compounded and used according to the mass ratio of 1, heavy metal ions in the extraction liquid can be precipitated more thoroughly, the precipitation rate is high, the sludge amount is small, and the precipitation rate is highest when the mass ratio is 3: 1.
Preferably, the volume ratio of the precipitant to the extraction liquid is (0.1-1): 10. The precipitant is added according to the proportion for precipitation, so that the heavy metal ions in the extract can be precipitated more thoroughly.
Has the advantages that: the invention firstly utilizes the organic extractant with higher extraction rate to extract the heavy metal in the pickling waste liquid, achieves the aim of removing the heavy metal in the pickling waste liquid, reduces the amount of the heavy metal-containing waste liquid, and then utilizes the precipitator to precipitate and separate out the heavy metal ions in the extraction liquid, thereby reducing the dosage of the precipitator and realizing the recycling of the extractant. The method can effectively remove heavy metals in the pickling waste liquid, and has the advantages of simple treatment process, low cost, environmental protection and no pollution.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention is further illustrated by the following examples. It is apparent that the following examples are only a part of the embodiments of the present invention, and not all of them. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. The raw materials used in the examples of the present invention can be purchased commercially, wherein the YQ-0002 precipitant is obtained from Yuqi chemical Co., Ltd, Guangzhou, and the DTC precipitant is obtained from Nasen water treatment agent Co., Ltd, Guangzhou.
Example 1
A method for extracting and separating heavy metals in pickle liquor comprises the following steps: adding an organic extractant into the pickling waste liquid for extraction, fully oscillating in an oscillator to achieve extraction balance, standing for layering to obtain an organic phase containing heavy metal ions; the organic phase was stirred at 100RPM for 0.5h with a precipitant added and the precipitate separated.
In the embodiment, the organic extractant comprises the following components in percentage by weight: 15% of 2-ethylhexyl phosphate mono-2-ethylhexyl ester, 15% of tributyl phosphate, 5% of polyaspartic acid and the balance of sulfonated kerosene. The volume ratio of the organic extractant to the pickling waste liquid is 1: 5. The precipitator is a mixture of YQ-0002 precipitator and DTC precipitator, and the mass ratio of the YQ-0002 precipitator: DTC precipitant is 3: 1. The volume ratio of the precipitant to the extract is 0.5: 10.
Example 2
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the organic extractant comprises the following components in percentage by weight: 10% of 2-ethylhexyl phosphate mono-2-ethylhexyl ester, 10% of tributyl phosphate, 10% of polyaspartic acid and the balance of sulfonated kerosene.
Example 3
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the organic extractant comprises the following components in percentage by weight: 20% of 2-ethylhexyl phosphate mono-2-ethylhexyl ester, 20% of tributyl phosphate, 1% of polyaspartic acid and the balance of sulfonated kerosene.
Example 4
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the volume ratio of the organic extractant to the pickling waste liquid is 1: 4.
Example 5
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the volume ratio of the organic extractant to the pickling waste liquid is 1: 6.
Example 6
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the precipitator is a mixture of YQ-0002 precipitator and DTC precipitator, and the mass ratio of the YQ-0002 precipitator: DTC precipitant 2: 1.
Example 7
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the precipitator is a mixture of YQ-0002 precipitator and DTC precipitator, and the mass ratio of the YQ-0002 precipitator to the DTC precipitator is as follows: DTC precipitant is 4: 1.
Example 8
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the volume ratio of the precipitating agent to the extraction liquid is 0.1: 10.
Example 9
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the volume ratio of the precipitating agent to the extraction liquid is 1: 10.
Comparative example 1
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the organic extractant comprises the following components in percentage by weight: 17.5 percent of 2-ethylhexyl phosphate, 17.5 percent of tributyl phosphate and the balance of sulfonated kerosene.
Comparative example 2
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the organic extractant comprises the following components in percentage by weight: 25% of tributyl phosphate, 10% of polyaspartic acid and the balance of sulfonated kerosene.
Comparative example 3
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the precipitant is YQ-0002 precipitant.
Comparative example 4
The method for extracting and separating the heavy metals in the pickle liquor only differs from the embodiment 1 in that: the precipitant is DTC precipitant.
And (3) effect testing:
the method of the embodiment 1 to 9 and the comparative example 1 to 4 are used for treating the pickling waste liquid, and the heavy metal indexes of the pickling waste liquid are as follows: chromium-containing 50.10PPM, nickel-containing 43.28PPM, copper-containing 21.09PPM and pH value of 1.3. The contents of heavy metal ions in the raffinate and the separated and precipitated organic phase obtained by the respective methods were measured, and the results are shown in the following table.
Figure BDA0002586984750000051
Figure BDA0002586984750000061
Note: in the table, "-" indicates that the item was not detected.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (4)

1. The method for extracting and separating heavy metals from pickling waste liquid is characterized by comprising the following steps: adding an organic extractant into the pickling waste liquid for extraction to obtain an extraction liquid containing heavy metal ions; adding a precipitator into the extract liquor to precipitate heavy metals, and separating precipitates;
the organic extractant comprises the following components in percentage by weight: 15% of 2-ethylhexyl phosphate mono-2-ethylhexyl ester, 15% of tributyl phosphate, 5% of polyaspartic acid and the balance of sulfonated kerosene; the precipitant is a mixture of YQ-0002 precipitant and DTC precipitant; in the precipitator, the mass ratio of YQ-0002 precipitator to DTC precipitator is (2-4) to 1;
removing trivalent chromium ions, divalent nickel ions or copper ions by a method of extracting and separating heavy metals in the pickling waste liquid.
2. The method for extracting and separating heavy metals from pickling waste liquid according to claim 1, wherein the volume ratio of the organic extracting agent to the pickling waste liquid is 1 (4-6).
3. The method for extracting and separating heavy metals from pickling waste liquid according to claim 1, wherein the mass ratio of YQ-0002 precipitant to DTC precipitant in the precipitant is 3: 1.
4. The method for extracting and separating the heavy metals in the pickling waste liquid according to claim 1, wherein the volume ratio of the precipitator to the extraction liquid is (0.1-1): 10.
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