CN111196618A

CN111196618A - A method for removing cobalt ions and/or antibiotics in wastewater

Info

Publication number: CN111196618A
Application number: CN202010183553.0A
Authority: CN
Inventors: 程辉彩; 方楠; 何强
Original assignee: Institute of Biology of Hebei Academy of Sciences
Current assignee: Institute of Biology of Hebei Academy of Sciences
Priority date: 2020-03-16
Filing date: 2020-03-16
Publication date: 2020-05-26
Anticipated expiration: 2040-03-16
Also published as: CN111196618B

Abstract

The invention relates to a method for removing cobalt ions and/or antibiotics in wastewater, which comprises the following steps: (1) firstly, detecting the concentration of cobalt ions and/or antibiotics in the wastewater; (2) adding a composite material into the wastewater, and uniformly mixing the materials at room temperature; (3) continuously oscillating for 10 min-10 h; (4) centrifuging or filtering, separating the precipitate, and performing further harmless treatment and recovery treatment on the precipitate; the composite material is prepared by mixing 40-65 parts by weight of iron tailing sand micro powder and 35-60 parts by weight of steel slag micro powder. The method has the advantages of simple process, low cost, strong operability and wide application prospect.

Description

Method for removing cobalt ions and/or antibiotics in wastewater

Technical Field

The invention relates to the technical field of environmental water pollution treatment, in particular to a method for removing cobalt ions and/or antibiotics in wastewater.

Background

With the rapid development of social industrialization, a large amount of heavy metals enter an ecosystem in various industrial production processes, so that serious environmental pollution and resource waste are caused. Cobalt ions are one of the common toxic and harmful heavy metal substances in the waste, and the toxicity of the cobalt ions is higher than that of mercury, cadmium, lead, arsenic and chromium, and is second to methyl mercury. Meanwhile, the concentration range of the toxic effect generated by cobalt is very low, and the cobalt has biological accumulation and is extremely difficult to degrade and eliminate. With the increasing use of cobalt, cobalt and compounds thereof enter the environment in large quantities, and have serious threats to human health. Therefore, cobalt and compounds thereof are listed in a water body priority control pollutant blacklist and a monitoring index system of the national surface water environmental quality standard.

In addition, with the wide application of antibiotics in the fields of human medicine, agricultural production, livestock raising, aquaculture and the like, a large amount of antibiotics enter the environment through different routes and are accumulated in the environment. Antibiotics are difficult to metabolize after entering the human or animal body and most still enter the aqueous environment in the form of the parent compound. Antibiotics are detected in surface water, underground water and even drinking water at present, and the antibiotics remained in the water can cause harm to various organisms and induce drug resistance, so that the ecological environment safety and the human health are threatened.

At present, the method for treating cobalt ions in water mainly comprises the following steps: adsorption, chemical precipitation, ion exchange, electrolytic reduction, membrane separation, and the like. The adsorption method mostly adopts activated carbon for adsorption, but the cost is relatively high; the chemical precipitation method mainly comprises the steps of adding an alkaline preparation and the like, so that secondary pollution and cobalt resource waste are easily caused; the membrane separation technology has high cost, small flux and complex operation process; the costs of the ion exchange method, electrolytic reduction, and the like are also relatively high. The method for removing the antibiotics in the water body mainly comprises an advanced oxidation method, a photodegradation method, a biodegradation method and the like, but each method has obvious limitations. Therefore, the preparation of the high-efficiency and low-cost cobalt ion and antibiotic removing material becomes a research hotspot for relieving and treating the pollution of cobalt and antibiotics in the water body.

Disclosure of Invention

The invention aims to provide a method for removing cobalt ions and/or antibiotics in wastewater, which has the advantages of simple process, low cost, easy separation and strong operability.

The invention adopts the following technical scheme:

a method for removing cobalt ions and/or antibiotics from wastewater, comprising the steps of:

(1) firstly, detecting the concentration of cobalt ions and/or antibiotics in the wastewater;

(2) adding a composite material into the wastewater, and uniformly mixing the materials at room temperature;

(3) continuously oscillating for 10 min-10 h;

(4) centrifuging or filtering, separating the precipitate, and performing further harmless treatment and recovery treatment on the precipitate.

The composite material is prepared by mixing 40-65 parts by weight of iron tailing sand micro powder and 35-60 parts by weight of steel slag micro powder.

Wherein, 1 g of the composite material can remove at least 50 mg of cobalt ions in each liter of wastewater.

Particularly, in each liter of wastewater, 50-60 mg of cobalt ions can be removed by 1 g of the composite material.

Wherein, in each liter of wastewater, 1 g of the composite material can remove at least 5mg of antibiotics.

Particularly, in each liter of wastewater, 5-7 mg of antibiotics can be removed by 1 g of the composite material.

Wherein, in each liter of wastewater, 1.6-1.8 g of the composite material can remove at least 50 mg of cobalt ions and 5mg of antibiotics simultaneously.

Particularly, in each liter of wastewater, 1.6-1.8 g of the composite material can at least simultaneously remove 50-60 mg of cobalt ions and 5-7 mg of antibiotics.

Wherein the antibiotic comprises quinolone antibiotics, tetracycline antibiotics or sulfonamide antibiotics. Such as Ciprofloxacin (CIP), tetracycline, sulfadiazine, etc., said antibiotics being present in the form of soluble aqueous solutions.

The iron tailing sand micro powder and the steel slag micro powder are respectively obtained by ball milling and crushing the iron tailing sand and the steel slag and then sieving the crushed iron tailing sand and the steel slag through a 100-mesh sieve.

Wherein the iron tailing sand is solid waste discharged after grinding iron ore and selecting useful components, and the steel slag is a by-product of converter steelmaking or waste steelmaking melted in an electric arc furnace.

Wherein when only cobalt ions are contained in the step (1), the continuous oscillation time of the step (3) is 10-30 min.

Wherein when the antibiotics are contained in the step (1), the continuous oscillation time of the step (3) is 5-10 h.

Wherein, when only cobalt ions are contained in the step (1), the harmless treatment and recovery treatment process of the step (4) is as follows: drying the separated precipitate, adding a hydrochloric acid or sulfuric acid solution with the pH of 1-2, immersing the solid, shaking and uniformly mixing for 30min, and carrying out solid-liquid separation; and (4) repeatedly pickling for 2-3 times, and drying to obtain the recycled composite material.

And (2) when only antibiotics are contained in the step (1), drying the separated precipitate, treating at 100-200 ℃ for 1h, and cooling to room temperature to obtain the recycled composite material.

Wherein when the step (1) contains cobalt ions and antibiotics, the harmless treatment and recovery treatment process of the step (4) is as follows:

(a) drying the separated precipitate, treating at 100-200 ℃ for 1h, and cooling to room temperature;

(b) adding a hydrochloric acid or sulfuric acid solution with the pH value of 1-2 into the solid obtained by the treatment in the step (a), immersing the solid, shaking and uniformly mixing for 30min, and carrying out solid-liquid separation;

(c) and (c) repeating the acid washing and water washing processes in the step (b) for 2-3 times respectively, and drying to obtain the recycled composite material.

The invention has the beneficial effects that: the raw materials of the composite material mainly comprise iron tailing sand and steel slag, the solid waste is large in amount, cheap and easy to obtain, and the cobalt ions and antibiotics in the wastewater are treated by the composite material, so that the treatment of the waste by the waste is equivalent to the treatment of the waste by the waste, the waste is changed into the valuable, and the treatment cost is obviously reduced. Secondly, cobalt ions in the wastewater are removed by using the iron tailing sand composite material, only 10-30 min is needed, only 5-10 h is needed for treating antibiotics, the method is rapid and efficient, and the precipitate is easy to separate. Thirdly, the composite material after recovering the cobalt ions can be recycled. Meanwhile, the antibiotics can be recovered after high-temperature inactivation, so that secondary pollution is avoided.

The invention mainly utilizes the solid wastes of iron tailing sand and steel slag to process and prepare the composite material for removing cobalt ions and antibiotics in the wastewater, is an effective way for treating wastes with wastes, obviously reduces the treatment cost while removing the cobalt ions and the antibiotics in the wastewater, and has the advantages of cheap and easily obtained raw materials, simple operation and wide application prospect.

Detailed Description

The embodiments of the present invention are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Unless otherwise defined, terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Further, it will be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense.

Example 1

The iron tailing sand composite material is prepared by drying, ball-milling and crushing the following raw materials in parts by weight, sieving with a 100-mesh sieve and mixing: 65 parts of iron tailing sand micro powder and 35 parts of steel slag micro powder.

Wherein the iron tailing sand is from Wuan city of Handan, Hebei province, the steel slag is from steelmaking waste tailings refined in Zhang Jiakou city, and the main chemical components of the iron tailing sand are shown in Table 1.

Table 1 main chemical composition of iron tailings sand used in example 1

。

Example 2

The iron tailing sand composite material is prepared by drying, ball-milling and crushing the following raw materials in parts by weight, sieving with a 100-mesh sieve and mixing: 50 parts of iron tailing sand micro powder and 50 parts of steel slag micro powder.

The iron tailing sand comes from the sand river city of the chentai city of the north river, the steel slag comes from the waste tailings of steelmaking popularized in the Shujiakou city, and the main chemical components of the iron tailing sand are shown in the table.

Table 2 main chemical composition of iron tailings sand used in example 2

。

Example 3

The iron tailing sand composite material is prepared by drying, ball-milling and crushing the following raw materials in parts by weight, sieving with a 100-mesh sieve and mixing: 40 parts of iron tailing sand micro powder and 60 parts of steel slag micro powder.

The iron tailing sand is from Laiyuan county of Baoding city, Hebei province, the steel slag is from steelmaking waste tailings announced in Zhang Jiakou city, and the main chemical components of the iron tailing sand are shown in Table 3:

table 3 main chemical composition of iron tailings sand used in example 3

。

Examples 4 to 12

Preparing cobalt-containing ions (0-1000 mg/L), antibiotics (0-100 mg/L) and mixed wastewater of the cobalt-containing ions and the antibiotics with different concentrations, wherein the loading amount of each container is 1L, and treating the wastewater by adopting iron tailing sand composite materials with different amounts and different configurations respectively, wherein the specific application is shown in Table 4. According to the contents of cobalt ions and antibiotics in various embodiments, a certain amount of composite material is properly added, the addition amount of the composite material can refer to the removal amount of cobalt in each g of solution being not less than 50 mg, the removal amount of the antibiotic being not less than 5mg, and when the wastewater contains both the cobalt ions and the antibiotic, 1.6g to 1.8 g of the composite material can remove not less than 50 mg of cobalt ions and not less than 5mg of the antibiotic. After the composite material is added into a solution containing cobalt ions and/or antibiotics at room temperature (10-35 ℃), continuously shaking and uniformly mixing for 10-30 min or 5-10 h, wherein only cobalt ion-containing wastewater is treated for 10-30 min, and the antibiotics-containing wastewater or the mixed wastewater of the cobalt ion-containing wastewater and the antibiotics-containing wastewater is treated for 5-10 h. The results shown in table 4 show that the removal rate of the composite material to cobalt ions and/or antibiotics in the water body is greater than 95%.

TABLE 4 iron tailings sand composite results for treatment of cobalt and/or antibiotic containing wastewater

。

Example 13

And precipitating or filtering the composite material treated by the cobalt ions and/or the antibiotics in the embodiment 7-9, and airing or drying. In example 7, only cobalt ions are treated, hydrochloric acid or sulfuric acid solution with the pH of 1-2 is added into the treated composite material, the liquid is soaked by about 2cm of the solid, the solid and the liquid are uniformly stirred for 30min, solid and liquid are separated, the solid is washed by water, the acid washing and the water washing are repeated for 2-3 times, and the cobalt ions in the liquid can be recovered. In example 8, after the composite material for treating the antibiotics is dried and treated at 150 ℃ for 1h, the antibiotics are inactivated, and the composite material can be recycled. In example 9, the composite material for treating the mixed liquid of cobalt ions and antibiotics can be dried, and treated at high temperature to inactivate the antibiotics (at 150 ℃ for 1 h), and then treated with an acid solution to recover the cobalt ions.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. a method for removing cobalt ions and/or antibiotics in waste water, is characterized in that, it comprises the steps:

(1) First detect the concentration of cobalt ions and/or antibiotics in wastewater;

(2) Add the composite material to the waste water, shake and mix at room temperature;

(3) Continue to shake for 10 min to 10 h;

(4) Centrifugation or filtration to separate the precipitate, and further harmless treatment and recovery of the precipitate;

The composite material comprises 40-65 parts by weight of iron tailings fine powder and 35-60 parts by weight of steel slag fine powder.

2. a kind of method for removing cobalt ion and/or antibiotic in waste water according to claim 1, is characterized in that, in every liter of waste water, 1 g composite material can remove the cobalt ion of 50 mg or the cobalt ion of 5 mg at least. antibiotic.

3. a kind of method for removing cobalt ion and/or antibiotic in waste water according to claim 1, is characterized in that, in every liter of waste water, 1.6～1.8 g composite material can remove the cobalt ion of 50 mg and 50 mg at least. mg antibiotics.

4. A method for removing cobalt ions and/or antibiotics in wastewater according to claim 1, wherein the antibiotics comprise quinolones, tetracyclines or sulfonamide antibiotics.

5. a kind of method for removing cobalt ions and/or antibiotics in waste water according to claim 1, is characterized in that, described iron tailings sand micropowder and steel slag micropowder are respectively by iron tailings sand and steel slag by ball milling after grinding. 100 mesh sieve to obtain.

6. A method for removing cobalt ions and/or antibiotics in wastewater according to claim 1, wherein when only cobalt ions are contained in the step (1), the continuous shaking time of the step (3) 10 to 30 minutes.

7. A method for removing cobalt ions and/or antibiotics in wastewater according to claim 1, wherein when antibiotics are contained in the step (1), the continuous shaking time of the step (3) is 5 ~10 hours.

8 . The method for removing cobalt ions and/or antibiotics in wastewater according to claim 1 , wherein when only cobalt ions are contained in the step (1), no The process of detoxification treatment and recovery treatment is as follows: after the separated precipitate is dried, add hydrochloric acid or sulfuric acid solution with pH 1~2, immerse the solid, shake and mix for 30 min, and separate the solid and liquid; repeat pickling and water washing for 2 times each. ~3 times, air-dry or tumble dry recycled composites.

9. A method for removing cobalt ions and/or antibiotics in wastewater according to claim 1, wherein when only antibiotics are contained in the step (1), after the separated precipitate is dried, Treated at 100-200 ℃ for 1 h, cooled to room temperature, and recovered the composite material.

10. A method for removing cobalt ions and/or antibiotics in wastewater according to claim 1, wherein when the step (1) contains cobalt ions and antibiotics, the step (4) The harmless treatment and recycling process is as follows:

(a) The separated precipitate was dried, treated at 100-200 °C for 1 h, and cooled to room temperature;

(b) adding a solution of hydrochloric acid or sulfuric acid with a pH of 1 to 2 to the solid obtained in step (a), immersing the solid, shaking and mixing for 30 min, and separating the solid from the liquid;

(c) Repeat the pickling and water washing process of step (b) for 2 to 3 times, and then dry and recycle the composite material.