Application of manganese-titanium composite adsorbent in the adsorption and removal of antimony in textile printing and dyeing wastewater

Abstract

This invention discloses the application of a manganese-titanium composite adsorbent in the adsorption and removal of antimony in textile dyeing and printing wastewater, belonging to the field of environmental adsorbent technology. The application includes the following steps: first, adjusting the pH of the textile dyeing and printing wastewater to 3.0~10.0; then adding the manganese-titanium composite adsorbent to the wastewater and stirring for 1~5 h; the preparation method of the manganese-titanium composite adsorbent includes the following steps: S1, adding manganese nitrate, tetrabutyl titanate, propylene oxide, and epichlorohydrin to ethanol and stirring until uniformly mixed to obtain a precursor solution; S2, adding water to the precursor solution and stirring until uniformly mixed, then allowing it to stand at 40 ℃~60 ℃ for 12~36 hours to obtain a gel; S3, calcining the gel to obtain the manganese-titanium composite adsorbent. This invention uses propylene oxide and epichlorohydrin as auxiliaries to prepare the manganese-titanium composite adsorbent, which, when used to adsorb and remove antimony from textile dyeing and printing wastewater, achieves a removal rate of over 99%.

Description

Technical Field

[0001] This invention belongs to the field of environmental adsorbent technology, and more specifically, relates to the application of manganese-titanium composite adsorbent in the adsorption and removal of antimony in textile printing and dyeing wastewater. Background Technology

[0002] Antimony (Sb) is an important rare metal with wide applications in alloys, semiconductors, and chemicals due to its unique physical and chemical properties. In the environment, Sb exists in multiple forms, with Sb(III) and Sb(V) being the most prevalent oxidized states. Changes in environmental factors and redox conditions alter the chemical form of Sb and affect its migration and transformation in environmental media. Different chemical forms of Sb determine its toxicity, with Sb(III) being significantly more toxic than Sb(V). Sb and its compounds can bind to sulfhydryl groups in animals or humans, interfering with enzyme activity and disrupting intracellular ion balance, leading to hypoxia. Sb can also be toxic to plants, causing stunted growth, inhibited photosynthesis, and preventing the absorption of certain essential elements and the synthesis of certain metabolites. In recent years, considerable concentrations of antimony have been detected in both groundwater and surface water in my country, prompting increasing attention from scholars on how to remove antimony from water.

[0003] Currently, the main technologies for removing antimony-containing wastewater include chemical treatment, adsorption, electrochemical methods, ion exchange, biological treatment, and membrane separation. Among these, adsorption utilizes materials with good adsorption properties (such as activated carbon fiber, activated alumina, zeolite molecular sieves, and chelating exchange resins) to adsorb antimony from the wastewater onto the material surface, thereby achieving antimony removal. Adsorption has advantages such as high antimony removal efficiency, simple operation, and moderate cost, and is considered one of the most practical technologies for removing antimony-containing wastewater. However, the regeneration and treatment of the adsorbent after use need to be considered.

[0004] Chinese patent publication number CN115445568A discloses a composite adsorbent for antimony removal, its preparation method, and its uses. This composite adsorbent comprises an Fe2O3 matrix and a supported MnFe2O4 adsorbent material. Chinese patent publication number CN108262002A discloses a preparation method and application of an Fe-Ti binary oxide adsorbent for antimony removal, using iron salts and titanium salts as raw materials.

[0005] However, the active component of the adsorbent in the aforementioned patents is mainly iron oxide, and in practical applications, it has been found that there is still room for improvement in antimony removal efficiency. To achieve cost reduction and efficiency improvement in the process of ensuring compliant discharge of textile dyeing and printing wastewater, it is urgent to develop a more efficient antimony removal adsorbent to improve the antimony removal rate in textile dyeing and printing wastewater. Summary of the Invention

[0006] 1. The problem to be solved

[0007] Addressing the technical problem that most existing antimony removal adsorbents, which primarily use iron oxide as the active component, still have room for improvement in antimony removal efficiency, this invention has accidentally discovered that a manganese-titanium composite adsorbent prepared using propylene oxide and epichlorohydrin as auxiliaries can effectively adsorb and remove antimony from textile dyeing wastewater, which is of great significance for promoting the compliant discharge of textile dyeing wastewater.

[0008] 2. Technical Solution

[0009] To solve the above problems, the technical solution adopted by the present invention is as follows:

[0010] [1. Application of manganese-titanium composite adsorbent in the adsorption and removal of antimony in textile printing and dyeing wastewater]

[0011] The first aspect of this invention provides the application of a manganese-titanium composite adsorbent in the adsorption and removal of antimony in textile dyeing wastewater, the application comprising the following steps:

[0012] First, adjust the pH value of the textile printing and dyeing wastewater to 3.0~10.0, preferably 4.0~8.0;

[0013] Add manganese-titanium composite adsorbent to the textile printing and dyeing wastewater and stir for 1-5 h, preferably 2-4 h.

[0014] The preparation method of manganese-titanium composite adsorbent includes the following steps:

[0015] S1. Add manganese nitrate, tetrabutyl titanate, propylene oxide and epichlorohydrin to ethanol and stir until they are mixed evenly to obtain a precursor solution.

[0016] S2. Add water to the precursor solution and stir to mix evenly. Let stand at 40 ℃~60 ℃ for 12~36 hours to obtain a gel.

[0017] S3. The gel was calcined to obtain a manganese-titanium composite adsorbent.

[0018] The first aspect of this invention provides the application of a manganese-titanium composite adsorbent in the adsorption and removal of antimony in textile dyeing and printing wastewater, achieving an antimony removal rate of over 99% with high efficiency. Furthermore, the method is simple to operate, with low leaching concentration of manganese ions during the antimony removal process and minimal secondary pollution, demonstrating the excellent stability of the manganese-titanium composite adsorbent. It is recyclable, and the cost of antimony removal is low, which is beneficial for achieving cost reduction and efficiency improvement in the process of achieving compliant discharge of textile dyeing and printing wastewater.

[0019] During the preparation of manganese-titanium composite adsorbent, it was accidentally discovered that using a mixture of propylene oxide and epichlorohydrin as an auxiliary agent to prepare the manganese-titanium composite adsorbent significantly improved the antimony removal rate when used to adsorb and remove antimony from textile dyeing wastewater. Moreover, the manganese-titanium composite adsorbent has excellent stability, which not only reduces secondary pollution to textile dyeing wastewater but also allows for recycling, thus reducing the cost of antimony removal from textile dyeing wastewater.

[0020] Furthermore, manganese nitrate, as the active component precursor, and tetrabutyl titanate, as the carrier precursor, can rapidly form manganese oxide and titanium dioxide binary oxide adsorbents after calcination, with fewer residual impurities such as nitrate, which is also conducive to further improving the adsorption and removal rate of antimony by the manganese-titanium composite adsorbent.

[0021] As a preferred embodiment of any technical solution of the first aspect of the present invention, the mass ratio of propylene oxide to epichlorohydrin in step S1 is 1:(0.5~1.5), preferably 1:(0.8~1.2), and most preferably 1:1.

[0022] As a preferred embodiment of any technical solution of the first aspect of the present invention, the mass ratio of manganese nitrate to ethanol in step S1 is 1:(16~80), preferably 1:(20~40), and most preferably (1.3~1.8):40;

[0023] The mass ratio of tetrabutyl titanate to ethanol is 1:(4~10), preferably 1:(6~8), and most preferably 3:20;

[0024] The total amount of propylene oxide and epichlorohydrin to ethanol is in a mass ratio of 1:(2~5), preferably 1:(3~4), and most preferably 3:10.

[0025] As a preferred embodiment of any technical solution of the first aspect of the present invention, the mass ratio of water to ethanol in step S2 is 1:(30~50).

[0026] Using water as a gelation promoter in the preparation process of manganese-titanium composite adsorbent not only facilitates the formation of uniform adsorbent material from manganese and titanium, but also reduces the cost of antimony adsorption and removal.

[0027] As a preferred embodiment of any technical solution in the first aspect of the present invention, the calcination temperature in step S3 is 150 ℃~250 ℃, preferably 180 ℃~220 ℃, and most preferably 200 ℃;

[0028] The roasting time is 2 to 6 hours, preferably 3 to 5 hours, and most preferably 4 hours.

[0029] As a preferred embodiment of any technical solution in the first aspect of the present invention, the mass concentration of the manganese-titanium composite adsorbent in the textile printing and dyeing wastewater is 0.05 g / L to 1 g / L, preferably 0.05 g / L to 0.5 g / L.

[0030] As a preferred embodiment of any technical solution in the first aspect of the present invention, the antimony concentration in the textile printing and dyeing wastewater is 0.5 mg / L to 10 mg / L, preferably 3 mg / L to 7 mg / L.

[0031] [2. Preparation method of manganese-titanium composite adsorbent]

[0032] The second aspect of this invention provides a method for preparing the manganese-titanium composite adsorbent used in the first aspect of this invention, comprising the following steps:

[0033] S1. Add manganese nitrate, tetrabutyl titanate, propylene oxide and epichlorohydrin to ethanol and stir until they are mixed evenly to obtain a precursor solution.

[0034] S2. Add water to the precursor solution and stir to mix evenly. Let stand at 40 ℃~60 ℃ for 12~36 hours to obtain a gel.

[0035] S3. The gel was calcined to obtain a manganese-titanium composite adsorbent.

[0036] As a preferred embodiment of any technical solution in the second aspect of the present invention, the mass ratio of propylene oxide to epichlorohydrin in step S1 is 1:(0.5~1.5), preferably 1:(0.8~1.2), and most preferably 1:1.

[0037] As a preferred embodiment of any technical solution in the second aspect of the present invention, the mass ratio of manganese nitrate to ethanol in step S1 is 1:(16~80), preferably 1:(20~40), and most preferably (1.3~1.8):40;

[0038] The mass ratio of tetrabutyl titanate to ethanol is 1:(4~10), preferably 1:(6~8), and most preferably 3:20;

[0039] The total amount of propylene oxide and epichlorohydrin to ethanol is in a mass ratio of 1:(2~5), preferably 1:(3~4), and most preferably 3:10.

[0040] As a preferred embodiment of any technical solution in the second aspect of the present invention, the mass ratio of water in step S2 to ethanol in step S1 is 1:(30~50).

[0041] As a preferred embodiment of any technical solution in the second aspect of the present invention, the calcination temperature in step S3 is 150 ℃~250 ℃, preferably 180 ℃~220 ℃, and most preferably 200 ℃;

[0042] The roasting time is 2 to 6 hours, preferably 3 to 5 hours, and most preferably 4 hours.

[0043] [3. Manganese-titanium composite adsorbent]

[0044] The third aspect of the present invention provides a manganese-titanium composite adsorbent used in the first aspect of the present invention. The manganese-titanium composite adsorbent includes an active component and a support, wherein the active component is a manganese oxide and the support is titanium dioxide.

[0045] The manganese-titanium composite adsorbent provided in the third aspect of the present invention uses titanium dioxide as a carrier and manganese oxide as an active ingredient to form a manganese-titanium binary oxide adsorbent. Combined with the special pore structure that the manganese-titanium composite adsorbent may have, it can effectively remove antimony from textile dyeing and printing wastewater.

[0046] As a preferred embodiment of any technical solution in the third aspect of the present invention, the loading of manganese oxide in the manganese-titanium composite adsorbent, based on manganese trioxide, is 20 wt.%~50 wt.%, preferably 30 wt.%~40 wt.%.

[0047] 3. Beneficial effects

[0048] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0049] (1) The application of the manganese-titanium composite adsorbent provided by this invention in the adsorption and removal of antimony in textile printing and dyeing wastewater achieves an antimony removal rate of over 99%, demonstrating high efficiency. Furthermore, the method is simple to operate, with low leaching concentration of manganese ions during the antimony removal process and minimal secondary pollution, indicating that the manganese-titanium composite adsorbent has excellent stability, can be recycled, and has low antimony removal costs. This is beneficial for achieving cost reduction and efficiency improvement in the process of achieving standard discharge of textile printing and dyeing wastewater, and is suitable for widespread industrial application.

[0050] (2) The preparation method of the manganese-titanium composite adsorbent for adsorbing and removing antimony in textile dyeing and printing wastewater provided by the present invention uses a mixture of propylene oxide and epichlorohydrin as an auxiliary agent. In particular, when the mass ratio of propylene oxide to epichlorohydrin in the mixture is 1:1, the antimony removal rate of the prepared manganese-titanium composite adsorbent is significantly improved when it is used to adsorb and remove antimony in textile dyeing and printing wastewater. Moreover, the manganese-titanium composite adsorbent has excellent stability, which not only reduces secondary pollution to textile dyeing and printing wastewater, but also allows for recycling, thereby reducing the cost of adsorbing and removing antimony from textile dyeing and printing wastewater.

[0051] (3) The manganese-titanium composite adsorbent provided by the present invention for adsorbing and removing antimony in textile dyeing wastewater uses titanium dioxide as a carrier and manganese oxide as an active ingredient to form a manganese-titanium binary oxide adsorbent. Combined with the special pore structure that the manganese-titanium composite adsorbent may have, it can effectively remove antimony in textile dyeing wastewater. Attached Figure Description

[0052] Figure 1 This is a schematic flowchart of the preparation method of the manganese-titanium composite adsorbent of the present invention;

[0053] Figure 2 The image shows an electron microscope image of the manganese-titanium composite adsorbent prepared in Example 1. Detailed Implementation

[0054] Unless otherwise defined, all 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 pertains.

[0055] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0056] Concentration, amount, and other numerical data may be presented in range format herein. It should be understood that such range format is used solely for convenience and brevity and should be flexibly interpreted to include not only the values ​​explicitly stated as the limits of the range, but also all individual values ​​or subranges encompassed within the range, as if each value and subrange were explicitly stated. For example, a numerical range of 1 to 4.5 should be interpreted to include not only the explicitly stated limits of 1 to 4.5, but also individual numbers (such as 2, 3, 4) and subranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges that describe only a single value, such as "less than 4.5," which should be interpreted to include all the aforementioned values ​​and ranges. Furthermore, this interpretation should apply regardless of the breadth of the range or characteristic described.

[0057] The present invention will be further described below with reference to specific embodiments.

[0058] It should be noted that the concentration of metal ions in the following specific embodiments is determined by inductively coupled plasma optical emission spectrometry (ICP-OES).

[0059] Materials used in preparation:

[0060] The manganese nitrate solution used in the examples is an aqueous solution with a manganese nitrate content of 50 wt.%.

[0061] Example 1

[0062] This embodiment describes a method for preparing a manganese-titanium composite adsorbent for antimony removal, such as... Figure 1 As shown, it includes the following steps:

[0063] S1. Add 2.7 g manganese nitrate solution, 6.0 g tetrabutyl titanate, 6.0 g propylene oxide and 6.0 g epichlorohydrin to 40 g ethanol and stir for 6 hours until the mixture is homogeneous to obtain the precursor solution.

[0064] S2. Add 1.0 g of water to the precursor solution and stir to mix evenly. Let stand at 50 °C for 24 hours to obtain a gel.

[0065] S3. The gel was calcined at 200 °C in air for 4 hours to obtain the manganese-titanium composite adsorbent, as shown in the electron micrograph. Figure 2 As shown. Based on manganese trioxide, the loading of manganese oxide in the manganese-titanium composite adsorbent is approximately 30 wt.% (calculated value is 29.8 wt.%), and this manganese-titanium composite adsorbent is designated as 30Mn-Ti-11.

[0066] Example 2

[0067] This embodiment is a method for preparing a manganese-titanium composite adsorbent for antimony removal. The difference from Example 1 is that the amount of manganese nitrate solution added in step S1 is changed to 3.6 g, and the amount of tetrabutyl titanate is changed to 5.1 g. The resulting manganese-titanium composite adsorbent, calculated as manganese trioxide, has a manganese oxide loading of 40 wt.%. This manganese-titanium composite adsorbent is denoted as 40Mn-Ti-11.

[0068] Comparative Example 1

[0069] This comparative example is a method for preparing a manganese-titanium composite adsorbent for antimony removal. The difference from Example 1 is that propylene oxide and epichlorohydrin are not added in step S1. The manganese-titanium composite adsorbent obtained has a manganese oxide loading of about 30 wt.% (calculated value is 29.8 wt.%) based on manganese trioxide. This manganese-titanium composite adsorbent is denoted as 30Mn-Ti-00.

[0070] Comparative Example 2

[0071] This comparative example is a method for preparing a manganese-titanium composite adsorbent for antimony removal. The difference from Example 1 is that epichlorohydrin is not added in step S1, and the amount of epichlorohydrin added is changed to 12.0 g. The manganese-titanium composite adsorbent obtained has a manganese oxide loading of about 30 wt.% (calculated value is 29.8 wt.%) based on manganese trioxide. This manganese-titanium composite adsorbent is denoted as 30Mn-Ti-10.

[0072] Comparative Example 3

[0073] This comparative example is a method for preparing a manganese-titanium composite adsorbent for antimony removal. The difference from Example 1 is that propylene oxide is not added in step S1, and the amount of epichlorohydrin added is changed to 12.0 g. The resulting manganese-titanium composite adsorbent, based on manganese trioxide, has a manganese oxide loading of approximately 30 wt.% (calculated value is 29.8 wt.%). This manganese-titanium composite adsorbent is designated as 30Mn-Ti-01.

[0074] Comparative Example 4

[0075] This comparative example describes a method for preparing a manganese-titanium composite adsorbent for antimony removal. The difference from Example 1 is that water is not added in step S2; the adsorbent is directly left to stand at 50 °C for 24 hours. Experimental results show that gel formation fails in step S2, therefore, a manganese-titanium composite adsorbent cannot be obtained for performance testing.

[0076] Test Example 1

[0077] This test example is used to test the antimony removal performance of the manganese-titanium composite adsorbents prepared in Examples 1-2 and Comparative Examples 1-3, respectively. The specific test steps are as follows:

[0078] 1. Prepare 150 mL of antimony solution with a concentration of 5 mg / L and place it in a glass beaker. Then add 0.5 mol / L dilute sulfuric acid to adjust the pH of the solution to 7.0.

[0079] 2. Add 0.1 g / L of manganese-titanium composite adsorbent to the above antimony-containing solution and stir for 3 hours. Then, measure the antimony concentration in the solution and calculate the antimony removal rate accordingly. At the same time, measure the leaching concentration of manganese ions in the solution to evaluate the stability of the manganese-titanium composite adsorbent.

[0080] The specific test results are shown in Table 1.

[0081] As shown in Table 1, the manganese-titanium composite adsorbent prepared in Example 1 removed 99.8% of the antimony from the wastewater under the given conditions and time, and the leaching concentration of manganese ions in the solution after adsorption was only 0.01 mg / L, demonstrating excellent adsorption performance and stability. Since propylene oxide and epichlorohydrin, used as additives in the preparation of the manganese-titanium composite adsorbent, left no residue after calcination, the compositions of the manganese-titanium composite adsorbents prepared in Example 1 and Comparative Examples 1-3 were basically the same. However, comparing the test results of Example 1 and Comparative Example 1, it can be found that although the manganese-titanium composite adsorbent of Comparative Example 1 was basically the same as that of Example 1, its antimony removal rate was only 88.3%, and its adsorption performance was far lower than that of the manganese-titanium composite adsorbent in Example 1. Comparing the test results of Example 1 and Comparative Examples 2-3, it can be found that only when propylene oxide and epichlorohydrin are used simultaneously as additives and a certain ratio is maintained between them can the adsorption and removal rate of antimony by the prepared manganese-titanium composite adsorbent be effectively improved.

[0082] Test Example 2

[0083] This test example is used to test the antimony removal performance of the manganese-titanium composite adsorbent prepared in Example 1. The specific test procedure differs from that in Example 1 in that the pH of the solution is adjusted to 5.0.

[0084] The specific test results are shown in Table 1.

[0085] As shown in Table 1, the manganese-titanium composite adsorbent prepared in Example 1 can also effectively adsorb and remove antimony at a pH of 5.0, indicating that the manganese-titanium composite adsorbent prepared in Example 1 has a wide applicable pH range for adsorbing and removing antimony.

[0086] Table 1. Adsorbent performance test results of Example 1 and Comparative Examples 1-3

[0087]

[0088] Test Example 3

[0089] This test example is used to evaluate the antimony removal performance of the manganese-titanium composite adsorbent prepared in Comparative Example 1. The specific test steps are as follows:

[0090] 1. Prepare 150 mL of antimony solution with a concentration of 5 mg / L and place it in a glass beaker. Then add 0.5 mol / L dilute sulfuric acid to adjust the pH of the solution to 7.0.

[0091] 2. Add 0.1 g / L of manganese-titanium composite adsorbent, 0.1 g of propylene oxide and 0.1 g of epichlorohydrin to the above antimony-containing solution and stir for 3 hours. Then measure the antimony concentration in the solution and calculate the antimony removal rate as 88.3%.

[0092] This test case shows that even the addition of propylene oxide and epichlorohydrin during the adsorption process cannot effectively improve the adsorption and removal rate of antimony by the manganese-titanium composite adsorbent.

[0093] The above description provides an illustrative overview of the present invention and its embodiments. This description is not restrictive, and the embodiments shown are merely one example of the invention's implementation. Actual implementations are not limited to these examples. Therefore, if those skilled in the art are inspired by this description and design similar implementations and examples without departing from the spirit of the invention, such designs should fall within the scope of protection of the present invention.

Claims

1. The application of manganese-titanium composite adsorbent in the adsorption and removal of antimony in textile printing and dyeing wastewater, characterized in that, The application includes the following steps: First, adjust the pH value of the textile printing and dyeing wastewater to 4.0~8.0; Then add manganese-titanium composite adsorbent to the textile printing and dyeing wastewater and stir for 1-5 hours; The preparation method of the manganese-titanium composite adsorbent includes the following steps: S1. Add manganese nitrate, tetrabutyl titanate, propylene oxide and epichlorohydrin to ethanol and stir until they are mixed evenly to obtain a precursor solution. S2. Add water to the precursor solution and stir to mix evenly. Let stand at 40 ℃~60 ℃ for 12~36 hours to obtain a gel. S3. The gel was calcined to obtain a manganese-titanium composite adsorbent.

2. The application of the manganese-titanium composite adsorbent according to claim 1 in the adsorption and removal of antimony in textile printing and dyeing wastewater, characterized in that, The mass ratio of propylene oxide to epichlorohydrin in S1 is 1:(0.5~1.5).

3. The application of the manganese-titanium composite adsorbent according to claim 1 in the adsorption and removal of antimony in textile printing and dyeing wastewater, characterized in that, In S1, the mass ratio of manganese nitrate to ethanol is 1:(16~80), the mass ratio of tetrabutyl titanate to ethanol is 1:(4~10), and the total amount of propylene oxide and epichlorohydrin to ethanol is 1:(2~5).

4. The application of the manganese-titanium composite adsorbent according to claim 1 in the adsorption and removal of antimony in textile printing and dyeing wastewater, characterized in that, The mass ratio of water in S2 to ethanol in S1 is 1:(30~50).

5. The application of the manganese-titanium composite adsorbent according to claim 1 in the adsorption and removal of antimony in textile printing and dyeing wastewater, characterized in that, The roasting temperature in S3 is 150 ℃~250 ℃, and the roasting time is 2~6 hours.

6. The application of the manganese-titanium composite adsorbent according to claim 5 in the adsorption and removal of antimony in textile printing and dyeing wastewater, characterized in that, The manganese-titanium composite adsorbent comprises an active component and a carrier, wherein the active component is a manganese oxide and the carrier is titanium dioxide.

7. The application of the manganese-titanium composite adsorbent according to claim 6 in the adsorption and removal of antimony in textile printing and dyeing wastewater, characterized in that, Based on manganese trioxide, the loading of manganese oxides in the manganese-titanium composite adsorbent is 20 wt.%~50 wt.%.

8. The application of the manganese-titanium composite adsorbent according to claim 1 in the adsorption and removal of antimony in textile printing and dyeing wastewater, characterized in that, The mass concentration of the manganese-titanium composite adsorbent in textile printing and dyeing wastewater is 0.05 g / L to 1 g / L.

9. The application of the manganese-titanium composite adsorbent according to any one of claims 1 to 8 in the adsorption and removal of antimony in textile printing and dyeing wastewater, characterized in that, The antimony concentration in the textile printing and dyeing wastewater is 0.5 mg / L to 10 mg / L.

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