Carbonized resin as well as preparation method and application thereof

Abstract

The invention provides carbonized resin as well as a preparation method and application thereof, and belongs to the technical field of wastewater treatment. The method comprises the following steps: drying and calcining waste ion exchange resin to obtain carbonized resin; and then the carbonized resin is used for wastewater treatment. The waste ion exchange resin is used as the raw material, the carbonized resin is prepared in one step through the pyrolysis carbonization method, and the preparation method is simple, easy to operate and low in cost. The carbonized resin prepared by the method can efficiently adsorb and remove pollutants such as dyes and antibiotics in wastewater, and can also efficiently catalyze persulfate to degrade organic pollutants in the wastewater, and the removal rate of COD (Chemical Oxygen Demand) in the wastewater reaches up to 90%.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and particularly relates to a carbonized resin, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, ion exchange resins have been widely used in industrial production. After the resin is saturated with adsorption, it can be regenerated by acid, alkali or salt solutions. However, due to the difficulty in eluting some impurities, the resin after multiple uses loses its original excellent performance due to the blockage of its pore structure and the loss of active sites, resulting in the difficulty of the effluent water quality to meet the treatment requirements. In this case, new resins are often replaced, generating waste resins. The waste resins after repeated use contain harmful substances such as toxic and harmful organic substances and heavy metals, and the proper treatment of these waste resins has become a problem.

[0003] Waste ion exchange resins belong to hazardous wastes and have high treatment costs, and their secondary utilization has become the focus of attention. These resins are difficult to degrade in the natural environment, and if not properly treated, they will pose a serious threat to the environment. Therefore, exploring an efficient method for the secondary utilization of waste resins not only helps to reduce costs, but also is an important measure to protect the environment. Summary of the Invention

[0004] The purpose of the present invention is to provide a carbonized resin, a preparation method thereof, and an application thereof, so as to solve the problem that waste ion exchange resins in the prior art cannot be secondarily recycled.

[0005] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a preparation method of a carbonized resin, comprising the following steps: drying and calcining waste ion exchange resins to obtain carbonized resins.

[0007] Preferably, the waste ion exchange resins include ion exchange resins used in hard water softening, desalted water, pure water or high-purity water preparation, hydrometallurgy, rare metal element separation or antibiotic extraction.

[0008] Preferably, the ion exchange resins include one or more of 001×10 cation exchange resins, D001 cation exchange resins, D113 cation exchange resins, D201 anion exchange resins and D301 cation resins.

[0009] Preferably, the drying temperature is 50-60°C.

[0010] Preferably, during the calcination treatment, the heating rate is 2-15°C / min, the calcination temperature is 400-800°C, and the calcination time is 1-3 h.

[0011] The present invention also provides a carbonized resin prepared by the preparation method of the carbonized resin described above.

[0012] The present invention also provides an application of the carbonized resin described above in wastewater treatment, and the carbonized resin can be placed in wastewater for treatment.

[0013] Preferably, the wastewater includes antibiotic wastewater or printing and dyeing wastewater; the addition amount of the carbonized resin is 100-5000 mg / L.

[0014] Preferably, when the wastewater is antibiotic wastewater, persulfate needs to be added; the mass ratio of the carbonized resin to persulfate is 1:0.1-1.

[0015] Preferably, the temperature of the treatment is 20-40 °C, and the treatment time is 60-180 min.

[0016] Advantages of the present invention:

[0017] The present invention uses waste ion exchange resin as raw material, and through pyrolytic carbonization method, a carbonized resin with rich specific surface area and stable structure is prepared in one step. The preparation method is simple, easy to operate and low in cost.

[0018] The carbonized resin prepared by the present invention can efficiently adsorb and remove pollutants such as dyes and antibiotics in wastewater, and can also efficiently catalyze the degradation of organic pollutants in wastewater by persulfate, and the COD removal rate in wastewater is as high as 90%.

[0019] The present invention not only realizes the resource utilization of waste ion exchange resin, but also can efficiently remove pollutants in water body, with low cost and high economic benefits, and has certain popularization and application prospects. Specific embodiments

[0020] The present invention provides a preparation method of a carbonized resin, including the following steps: drying and calcining the waste ion exchange resin to obtain the carbonized resin.

[0021] In the present invention, the waste ion exchange resin includes ion exchange resins used in hard water softening, desalted water, pure water or high-purity water preparation, hydrometallurgy, rare metal element separation or antibiotic extraction.

[0022] In the present invention, the waste ion exchange resin includes waste cation exchange resin or waste anion exchange resin; the waste cation exchange resin includes waste strong acid type cation exchange resin or waste weak acid type cation exchange resin; the waste anion exchange resin includes waste strong base type anion exchange resin or waste weak base type anion exchange resin.

[0023] In the present invention, the ion exchange resin includes one or several of 001×10 cation exchange resin, D001 cation exchange resin, D113 cation exchange resin, D201 anion exchange resin and D301 cation resin.

[0024] For the waste cation exchange resin containing metal ions, metal-carbon composite sites are formed during the preparation of the carbonized resin, which can provide more active sites for activating persulfate and promote the degradation of dyes and antibiotics in wastewater.

[0025] In the present invention, the drying temperature is 50-60°C, preferably 50°C, 55°C, 60°C.

[0026] In the present invention, during the calcination treatment, the heating rate is 2-15°C / min, preferably 5-12°C / min, more preferably 8-10°C / min; the calcination temperature is 400-800°C, preferably 500-700°C, more preferably 600-700°C; the calcination time is 1-3 h, preferably 1.5-2.5 h, more preferably 2 h.

[0027] In the present invention, after the calcination treatment, it is preferably washed, dried, ground and sieved, and the particle size of the carbonized resin after grinding is 10-75 μm.

[0028] The present invention also provides a carbonized resin prepared by the preparation method of the above-mentioned carbonized resin.

[0029] The present invention also provides an application of the above-mentioned carbonized resin in wastewater treatment, and the carbonized resin can be placed in wastewater for treatment.

[0030] In the present invention, the wastewater includes antibiotic wastewater or printing and dyeing wastewater; the addition amount of the carbonized resin is 100-5000 mg / L.

[0031] In the present invention, the antibiotics in the antibiotic wastewater include tetracycline, chloramphenicol or oxytetracycline, and the concentration of the antibiotics is 0.5-50 mg / L.

[0032] In the present invention, when the wastewater is antibiotic wastewater, persulfate needs to be added; the mass ratio of the carbonized resin to persulfate is 1:0.1-1.

[0033] In the present invention, the treatment temperature is 20-40°C, preferably 25-35°C, the treatment time is 60-180 min, preferably 90-150 min, more preferably 120 min.

[0034] The carbonized resin of the present invention can be used as an adsorbent to adsorb dyes and antibiotics in wastewater, and can also be used as a catalyst to catalytically activate persulfate to degrade dyes and antibiotics, realizing their mineralization and decomposition, and achieving the complete removal of dyes and antibiotics.

[0035] The technical solutions provided by the present invention will be described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0036] Example 1

[0037] The discarded 001×10 cation exchange resin used for softening pure water and repeatedly adsorbed and desorbed was dried at a temperature of 60°C, transferred to a crucible, and then placed in a tube furnace. The temperature was raised to 600°C at a heating rate of 8°C / min, and calcined for 2 h. The product after calcination was washed with deionized water, dried, ground into a uniform powder with a particle size of 10 - 75 μm, and passed through a 200-mesh sieve to obtain carbonized resin.

[0038] 0.2 g of the carbonized resin was added to 100 mL of methyl orange dye wastewater (COD = 200 mg / L). At 25°C, it was stirred at a speed of 150 rpm for 120 min, and a 96% reduction in the COD of the methyl orange dye wastewater could be achieved.

[0039] Example 2

[0040] The discarded D201 alkaline anion exchange resin used for softening pure water and repeatedly adsorbed and desorbed was dried at a temperature of 55°C, transferred to a crucible, and then placed in a tube furnace. The temperature was raised to 700°C at a heating rate of 10°C / min, and calcined for 2 h. The product after calcination was washed with deionized water, dried, ground into a uniform powder with a particle size of 10 - 75 μm, and passed through a 200-mesh sieve to obtain carbonized resin.

[0041] 0.3 g of the carbonized resin was added to 100 mL of wastewater containing tetracycline (the concentration of tetracycline was 20 mg / L). At 25°C, it was stirred at a speed of 150 rpm for 120 min, and a 94% reduction in the COD of the wastewater containing tetracycline could be achieved.

[0042] Example 3

[0043] The discarded D001 resin adsorbed with copper ions was dried at a temperature of 60°C, transferred to a crucible, and then placed in a tube furnace. The temperature was raised to 500°C at a heating rate of 8°C / min, and calcined for 2 h. The product after calcination was washed with deionized water, dried, ground into a uniform powder with a particle size of 10 - 75 μm, and passed through a 200-mesh sieve to obtain copper-doped carbonized resin.

[0044] Add 0.03 g of copper-doped carbonized resin to 100 mL of tetracycline-containing wastewater (where the concentration of tetracycline is 20 mg / L), then add 10 mg of sodium persulfate, and stir at 25 °C at a rotation speed of 150 rpm for 120 min, and a 90% reduction in the COD of the tetracycline-containing wastewater can be achieved.

[0045] Example 4

[0046] Dry the waste D001 resin adsorbed with iron ions at a temperature of 60 °C, transfer it to a crucible, then place it in a tube furnace, raise the temperature to 700 °C at a heating rate of 12 °C / min, keep it at this temperature for 2 h for calcination treatment, wash the product after calcination treatment with deionized water, dry it, grind it into a uniform powder with a particle size of 10 - 75 μm, and pass through a 200-mesh sieve to obtain iron-doped carbonized resin.

[0047] Add 0.02 g of iron-doped carbonized resin to 100 mL of tetracycline-containing wastewater (where the concentration of tetracycline is 30 mg / L), then add 20 mg of sodium persulfate, and stir at 25 °C at a rotation speed of 150 rpm for 120 min, and a 95% reduction in the COD of the tetracycline-containing wastewater can be achieved.

[0048] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can still be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a carbonized resin, characterized in that: The method comprises the following steps: drying and calcining the waste ion exchange resin to obtain the carbonized resin.

2. The method for preparing a carbonized resin according to claim 1, characterized in that: The waste ion exchange resin includes ion exchange resin that has been subjected to hard water softening, desalted water, pure water or high-purity water preparation, hydrometallurgy, separation of rare metal elements or extraction of antibiotics.

3. The method for preparing the carbonized resin according to claim 2, characterized in that: The ion exchange resin includes one or more of 001×10 cation exchange resin, D001 cation exchange resin, D113 cation exchange resin, D201 anion exchange resin and D301 cation exchange resin.

4. The method for preparing a carbonized resin according to any one of claims 1 to 3, characterized in that: The drying temperature is 50-60°C.

5. The method for preparing the carbonized resin according to claim 4, characterized in that: The heating rate during the calcination treatment is 2-15°C / min, the calcination treatment temperature is 400-800°C, and the calcination treatment time is 1-3h.

6. The carbonized resin obtained by the method for preparing a carbonized resin according to any one of claims 1 to 5.

7. Use of the carbonized resin according to claim 6 in wastewater treatment, characterized in that: The carbonized resin can be placed in wastewater for treatment.

8. The use of the carbonized resin in wastewater treatment according to claim 7, characterized in that: The wastewater includes antibiotic wastewater or printing and dyeing wastewater; the added amount of the carbonized resin is 100-5000 mg / L.

9. The use of the carbonized resin in wastewater treatment according to claim 8, characterized in that: When the wastewater is antibiotic wastewater, persulfate needs to be added; the mass ratio of the carbonized resin to the persulfate is 1:0.1-1.

10. Use of the carbonized resin in wastewater treatment according to claim 7 or 9, characterized in that: The treatment temperature is 20-40° C., and the treatment time is 60-180 min.