Sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals and sludge treatment method

Abstract

The present invention relates to the technical field of sludge treatment. Specifically, it relates to a sludge deep dehydration treatment agent for heterogeneous catalytic oxidation of sulfide minerals and a sludge treatment method. A sludge deep dehydration treatment agent for heterogeneous catalytic oxidation of sulfide minerals includes chalcopyrite and sodium percarbonate. The dehydration rate of the sludge treated by it can reach 94.9%, and it can synergistically reduce toxicity, with stable operating performance and lower cost. The sludge treatment method is as follows: adding the above-mentioned sludge deep dehydration treatment agent for heterogeneous catalytic oxidation of sulfide minerals into sludge with a rotation speed of 280 - 320 rpm and stirring for 20 - 50 min. The treated sludge is convenient and simple to dehydrate, and is suitable for industrial applications.

Description

Technical Field

[0001] The present invention relates to the technical field of sludge treatment. Specifically, it relates to a sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals and a sludge treatment method. Background Art

[0002] Efficient dehydration of sludge is an energy-saving and carbon-reducing process in sludge treatment in sewage treatment facilities. Due to the restrictive factor of hydrophilic extracellular polymer (EPS), weakening its hydrophilicity and water-holding capacity is crucial for achieving efficient sludge-water separation. The existing established α-Mn 2 O 3 +PMS treatment process for treating sludge can only achieve a minimum moisture content of the sludge cake of 71.8%. The existing established iron-rich biochar + PMS treatment process for treating sludge can only achieve a minimum moisture content of the sludge cake of 58.9%. There is an urgent need to develop a sewage treatment agent with a higher dehydration rate for sludge dehydration treatment. Summary of the Invention

[0003] An object of the present invention is to provide a sludge dehydrating agent, the dehydration rate of which for treating sludge can reach 94.9%, and it can synergistically reduce toxicity, has stable operating performance, and lower cost.

[0004] Another object of the present invention is to provide a sludge treatment method, the sludge treated by which is convenient and simple to dehydrate and is suitable for industrial applications.

[0005] The present invention solves its technical problems by adopting the following technical solutions.

[0006] The present invention provides a sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals, which includes chalcopyrite and sodium percarbonate.

[0007] Further, in some embodiments of the present invention, the mass ratio of the chalcopyrite to the sodium percarbonate is 100 - 600∶5 - 20.

[0008] Further, in some embodiments of the present invention, the mass ratio of the chalcopyrite to the sodium percarbonate is 200 - 500∶10 - 12.

[0009] Further, in some embodiments of the present invention, the mass ratio of the chalcopyrite to the sodium percarbonate is 500∶12.

[0010] Further, in some embodiments of the present invention, the chalcopyrite is pretreated before use, and the pretreatment is: crushing the chalcopyrite and sieving it to 140 - 160 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere.

[0011] Further, in some embodiments of the present invention, the main components of the chalcopyrite are CuFeS 2 , wherein the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%.

[0012] The present invention also provides a sludge treatment method, which adds the sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals described above into sludge with a rotation speed of 280 - 320 rpm and stirs for 20 - 50 min to obtain the treated sludge.

[0013] Further, in some embodiments of the present invention, the mass ratio of the sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals to the above sludge is 1∶2 - 10.

[0014] Further, in some embodiments of the present invention, the pH value of the sludge during treatment with the sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals is 2.5 - 6.

[0015] Further, in some embodiments of the present invention, the pH value of the sludge during treatment with the sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals is 3.

[0016] Further, in some embodiments of the present invention, the pH value of the above sludge is adjusted with sodium hydroxide solution or sulfuric acid solution.

[0017] A sludge dehydrating treatment agent according to an embodiment of the present invention has at least the following beneficial effects:

[0018] Using chalcopyrite and sodium percarbonate as the sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals can effectively assist sludge dehydration. The maximum dehydration rate of the sludge treated with chalcopyrite and sodium percarbonate as the sludge dehydrating agent for heterogeneous catalytic oxidation can reach 94.9%, the SRF can reach 0.96 ± 0.08×1012 m / kg, and the moisture content of the treated sludge cake is only 52.0 ± 0.9 wt%. While the dehydration rate of the untreated sludge is only 51.3%, and it can be known from experiments that the dehydration rate of the sludge treated only with chalcopyrite is only 83.4%, and the dehydration rate of the sludge treated only with sodium percarbonate is only 79.1%. For the existing established α-Mn 2 O 3 +PMS treatment process for treating sludge, the lowest moisture content of the sludge cake can only reach 71.8%, and for the existing established iron-rich biochar + PMS treatment process for treating sludge, the lowest moisture content of the sludge cake can only reach 58.9%, while the moisture content of the sludge cake treated with chalcopyrite and sodium percarbonate as the sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals is only 52.0 ± 0.9 wt%.

[0019] It has been found through research that chalcopyrite and sodium percarbonate can continuously generate a large amount of reactive oxygen species through a strong Fe and / or Cu cycle. The dominant reactive free radical ·OH and non-radical 1 O 2 can effectively degrade macromolecular EPS into low-molecular biological polymers, reduce the secondary structure of highly polar hydrophilic proteins, and reduce the water-holding interface affinity. Then, the electrostatic force and interfacial free energy are reduced, enhancing the self-flocculation and fluidity, thereby promoting the reduction of bound water and the efficiency of mud-water separation.

[0020] In addition, as can be seen from Test Examples 5 and 6, the sludge dewatering agent using this heterogeneous catalytic oxidation of sulfide minerals can also synergistically remove trichlocarban and resistance genes, etc., assisting in further detoxifying the sludge, achieving unexpected effects in the original sludge treatment.

[0021] A sludge treatment method according to an embodiment of the present invention has at least the following beneficial effects:

[0022] The sludge resistance ratio (SRF) of the sludge treated in Examples 16-18 and Comparative Example 6 is as Figure 4 shown. It can be seen therefrom that when the treatment time is 20-50 min, the dewatering performance of the sludge is better. If the time is too short or too long, the dewatering performance of the sludge is not good. When the treatment time is 30 min, the dewatering performance of the sludge reaches the best. This method is simple and convenient and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can also be obtained based on these drawings without creative efforts.

[0024] Figure 1 is the sludge resistance ratio of the sludge treated in Examples 1-6 and Comparative Example 1 of the present invention;

[0025] Figure 2 is the sludge resistance ratio of the sludge treated in Examples 5, 7-11 and Comparative Examples 2 and 3 of the present invention;

[0026] Figure 3 is the sludge resistance ratio of the sludge treated in Examples 12-15 and Comparative Examples 4 and 5 of the present invention;

[0027] Figure 4 is the sludge resistance ratio of the sludge treated in Examples 16-18 and Comparative Example 6 of the present invention;

[0028] Figure 5It is the detection result diagram of trichlocarban in Test Example 5 of the present invention;

[0029] Figure 6 It is the detection result diagram of resistance genes in Test Example 6 of the present invention. Detailed implementation manners

[0030] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. For those not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0031] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to specific embodiments.

[0032] The present invention provides a sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals, which includes chalcopyrite and sodium percarbonate.

[0033] Using chalcopyrite and sodium percarbonate as the sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals can effectively assist sludge dewatering. The sludge treated with chalcopyrite and sodium percarbonate as the sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals shows that the maximum dewatering rate can reach 94.9%, the SRF can reach 0.96 ± 0.08×1012 m / kg, and the moisture content of the treated sludge cake is only 52.0 ± 0.9 wt%. While the dewatering rate of the untreated sludge is only 51.3%, and from Comparative Example 1 and Comparative Example 2, it can be seen that the dewatering rate of the sludge treated only with chalcopyrite is only 83.4%, and the dewatering rate of the sludge treated only with sodium percarbonate is only 79.1%. For the existing established α-Mn 2 O 3 +PMS treatment process for treating sludge, the moisture content of the sludge cake can only reach 71.8% at the lowest. For the existing established iron-rich biochar + PMS treatment process for treating sludge, the moisture content of the sludge cake can only reach 58.9% at the lowest. While the moisture content of the sludge cake treated with chalcopyrite and sodium percarbonate as the sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals is only 52.0 ± 0.9 wt%.

[0034] When chalcopyrite and sodium percarbonate are used as sludge dehydrating agents for heterogeneous catalytic oxidation of sulfide minerals, sodium percarbonate reacts in the system according to reaction (1) to generate sodium carbonate and hydrogen peroxide; chalcopyrite reacts with oxygen in the system according to reaction (2) to decompose into ferrous ions, copper ions and sulfate ions; ferrous ions and copper ions react with hydrogen peroxide in the system according to reactions (3), (4), (5), (6), (7). Therefore, after chalcopyrite and sodium percarbonate are mixed, a large amount of active oxygen can be continuously generated through strong Fe and / or Cu cycles. As a result, the system is rich in active free radicals ·OH and non-free radicals 1 O 2 , effectively degrading macromolecular EPS into low-molecular biological polymers, reducing the secondary structure of highly polar hydrophilic proteins, and decreasing the water-holding interface affinity. Subsequently, the electrostatic force and interfacial free energy are reduced, enhancing the self-flocculation and fluidity, thereby promoting the reduction of bound water and the efficiency of mud-water separation.

[0035] Na 2 CO 3 ·1.5H 2 O 2 →Na 2 CO 3 +1.5H 2 O 2 (1)

[0036]

[0037] Fe 2+ +H 2 O 2 →Fe 3+ +OH - +·OH (3)

[0038]

[0039] Cu + +H 2 O 2 →Cu 2+ +OH - +·OH (5)

[0040]

[0041]

[0042] In addition, as can be seen from Test Examples 5 and 6, using this sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals can also synergistically remove trichlocarban and resistance genes, etc., assisting in further detoxifying the sludge and achieving unexpected effects in the original sludge treatment.

[0043] Further, in some embodiments of the present invention, the mass ratio of the chalcopyrite to the sodium percarbonate is 100 - 600∶5 - 20.

[0044] The sludge resistance ratios of the sludge after treatment in Examples 1 - 6 and Comparative Example 1 are as Figure 1 shown. It can be seen therefrom that as the usage amount of chalcopyrite increases from 0 to 600 mg / g TS, the SRF gradually increases from 48.8% to 81.6%. This indicates that as the usage amount of chalcopyrite increases, the dewaterability of the sludge is improved. The sludge resistance ratios of the sludge after treatment in Examples 5, 7 - 11 and Comparative Examples 2, 3 are as Figure 2 shown. It can be seen therefrom that when the usage amount of sodium percarbonate is 5 - 20 mg / g TS, the dewatering performance of the treated sludge is enhanced.

[0045] Further, in some embodiments of the present invention, the mass ratio of the chalcopyrite to the sodium percarbonate is 200 - 500∶10 - 12.

[0046] The sludge resistance ratios of the sludge after treatment in Examples 2 - 5 and Comparative Example 1 are as Figure 1 shown. It can be seen therefrom that when the usage amount of chalcopyrite is 200 - 500 mg / g TS, the dewatering performance of the sludge is higher. The sludge resistance ratios of the sludge after treatment in Examples 8, 9 and Comparative Examples 2, 3 are as Figure 2 shown. It can be seen therefrom that when the usage amount of sodium percarbonate is 10 - 12 mg / g TS, the dewatering performance of the treated sludge is stronger.

[0047] Further, in some embodiments of the present invention, the mass ratio of the chalcopyrite to the sodium percarbonate is 500∶12.

[0048] It can be Figure 1 seen that when the usage amount of chalcopyrite is 500 mg / g TS, the SRF reaches the best. When the usage amount of chalcopyrite exceeds 500 mg / g TS, the dewatering performance of the sludge begins to gradually decrease. This may be because too much chalcopyrite causes it to cover the active sites of sodium percarbonate.

[0049] It can be Figure 2 seen that when the usage amount of sodium percarbonate is greater than 12 mg / g TS, the sludge dewatering performance gradually decreases. This may be because when the usage amount of sodium percarbonate is relatively large, it will induce -OH scavenging, thus limiting the dewatering effect.

[0050] Further, in some embodiments of the present invention, the main component of the chalcopyrite is CuFeS 2 , wherein the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%.

[0051] Further, in some embodiments of the present invention, the above chalcopyrite is pretreated before use, and the pretreatment is as follows: crushing and sieving the chalcopyrite to 140 - 160 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere.

[0052] In this way, the utilization rate of the pretreated chalcopyrite is better. Finally, the treated chalcopyrite is stored in N 2 atmosphere to avoid the oxidation of the components in the chalcopyrite, which affects the subsequent use effect.

[0053] The present invention also provides a sludge treatment method, which uses the above-mentioned sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals and adds it to sludge with a rotation speed of 280 - 320 rpm and stirs for 20 - 50 min to obtain the treated sludge.

[0054] The sludge resistance ratio (SRF) of the sludge after treatment in Examples 16 - 18 and Comparative Example 6 is as Figure 4 shown. It can be seen therefrom that when the treatment time is 20 - 50 min, the dehydration performance of the sludge is better. If the time is too short or too long, the sludge dehydration performance is not good. When the treatment time is 30 min, the dehydration performance of the sludge reaches the best.

[0055] Further, in some embodiments of the present invention, the mass ratio of the dosage of the above-mentioned sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals to the above-mentioned sludge is 1∶2 - 10.

[0056] It can be seen from each example and the comparative example that such a ratio can make the sludge dehydration performance reach the best.

[0057] Further, in some embodiments of the present invention, the pH value of the sludge when using the above-mentioned sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals is 2.5 - 6.

[0058] It can be known from the sludge resistance ratio (SRF) of the sludge after treatment in Examples 12 - 15 and Comparative Examples 4 and 5 (refer to Figure 3 ) that when the pH value is 2.5 - 6, it is more helpful for the treatment of sludge by chalcopyrite and sodium percarbonate, and can further enhance the sludge dehydration rate. This is because the acidic environment not only facilitates the dissolution of Fe / Cu ions to generate active oxygen, but also amplifies the oxidation efficiency of active oxygen for EPS decomposition and the reduction of the ability to bind water.

[0059] Further, in some embodiments of the present invention, the pH value of the sludge when using the above-mentioned sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals is 3.

[0060] It can be known from the sludge resistance ratio (SRF) of the sludge after treatment in Examples 12 - 15 and Comparative Examples 4 and 5 (refer toFigure 3 ) When the pH value is 3, the dehydration rate of chalcopyrite and sodium percarbonate-treated sludge reaches the best.

[0061] Further, in some embodiments of the present invention, the pH value of the above-mentioned sludge is adjusted by sodium hydroxide solution or sulfuric acid solution.

[0062] The characteristics and performance of the present invention will be further described in detail below in conjunction with embodiments.

[0063] The sludge samples used in the examples and comparative examples of the present invention were collected from the secondary sedimentation tank of a sewage treatment plant in Guangzhou. Then, the samples were immediately transferred to the laboratory and stored in a refrigerator at 4°C. The main characteristics of the sludge are as follows: the water content is 97.2% ± 0.1, the total solids (TS) is 26.8 ± 0.1 g / L, the volatile solids (VS) is 13.1 ± 0.2 g / L, the SRF is 5.32 ± 0.11×1012 m / kg, and the pH value is 6.53 ± 0.19.

[0064] Natural chalcopyrite was purchased from a mining company in Yunnan, China. Chalcopyrite was characterized by scanning electron microscopy with energy chromatography (SEM-EDS, MIRA 3, Tescan, Czech Republic), X-ray diffraction (XRD, D8 Advance, Bruker, Germany), and X-ray photoelectron spectroscopy (XPS, K-AlpH value a, Thermo Fisher Scientific, USA). The characterization results of chalcopyrite confirmed that its main component is CuFeS2, and the elemental composition is Cu (33.22%), Fe (32.73%), and F (34.05%).

[0065] Example 1

[0066] This example provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0067] A sludge dewatering treatment agent provided in this example includes 100 g of chalcopyrite and 15 g of sodium percarbonate.

[0068] The main component of the above-mentioned chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. Before use, chalcopyrite is first pretreated. The above pretreatment is: crushing and sieving chalcopyrite to 140 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0069] This embodiment provides a sludge treatment method, in which the above-mentioned sludge dewatering agent is added to 885 g of sludge with a rotation speed of 300 rpm and stirred for 30 min. The pH value of the above-mentioned sludge is adjusted to 3.

[0070] Example 2

[0071] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0072] A sludge dewatering agent provided in this embodiment comprises 200 g of chalcopyrite and 15 g of sodium percarbonate.

[0073] The main component of the above-mentioned chalcopyrite is CuFeS 2 , wherein the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above-mentioned pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0074] This embodiment provides a sludge treatment method, in which the above-mentioned sludge dewatering agent is added to 785 g of sludge with a rotation speed of 280 rpm and stirred for 20 min. The pH value of the above-mentioned sludge is adjusted to 3 by using sodium hydroxide solution or sulfuric acid solution.

[0075] Example 3

[0076] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0077] A sludge dewatering agent provided in this embodiment comprises 300 g of chalcopyrite and 15 g of sodium percarbonate.

[0078] The main component of the above-mentioned chalcopyrite is CuFeS 2 , wherein the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above-mentioned pretreatment is: crushing and sieving the chalcopyrite to 160 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0079] This embodiment provides a sludge treatment method, in which the above-mentioned sludge dewatering agent is added to 685 g of sludge with a rotation speed of 320 rpm and stirred for 40 min. The pH value of the above-mentioned sludge is adjusted to 3.

[0080] Example 4

[0081] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0082] A sludge dewatering treatment agent provided in this embodiment includes 400 g of chalcopyrite and 15 g of sodium percarbonate.

[0083] The main components of the above chalcopyrite are CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0084] This embodiment provides a sludge treatment method, adding the above sludge dewatering treatment agent to sludge with a rotation speed of 300 rpm and stirring for 30 min. The pH value of the above sludge is adjusted to 3.

[0085] Example 5

[0086] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0087] A sludge dewatering treatment agent provided in this embodiment includes 500 g of chalcopyrite and 15 g of sodium percarbonate.

[0088] The main components of the above chalcopyrite are CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0089] This embodiment provides a sludge treatment method, adding the above sludge dewatering treatment agent to 485 g of sludge with a rotation speed of 300 rpm and stirring for 30 min. The pH value of the above sludge is adjusted to 3.

[0090] Example 6

[0091] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0092] A sludge dewatering treatment agent provided in this embodiment includes 600 g of chalcopyrite and 15 g of sodium percarbonate.

[0093] The main components of the above chalcopyrite are CuFeS2 , in which the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is as follows: The chalcopyrite is crushed and sieved to 150 μm, then it is subjected to ultrasonic treatment and pickling, and finally the treated chalcopyrite is stored in N 2 atmosphere and taken out when in use.

[0094] This embodiment provides a sludge treatment method, in which the above sludge dewatering agent is added to 385 g of sludge with a rotation speed of 300 rpm and stirred for 40 min. The pH value of the above sludge is adjusted to 3.

[0095] Example 7

[0096] This embodiment provides a sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals and a sludge treatment method.

[0097] A sludge dewatering agent provided in this embodiment includes 500 g of chalcopyrite and 5 g of sodium percarbonate.

[0098] The main component of the above chalcopyrite is CuFeS 2 , in which the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is as follows: The chalcopyrite is crushed and sieved to 150 μm, then it is subjected to ultrasonic treatment and pickling, and finally the treated chalcopyrite is stored in N 2 atmosphere and taken out when in use.

[0099] This embodiment provides a sludge treatment method, in which the above sludge dewatering agent is added to 485 g of sludge with a rotation speed of 300 rpm and stirred for 30 min. The pH value of the above sludge is adjusted to 3.

[0100] Example 8

[0101] This embodiment provides a sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals and a sludge treatment method.

[0102] A sludge dewatering agent provided in this embodiment includes 500 g of chalcopyrite and 10 g of sodium percarbonate.

[0103] The main component of the above chalcopyrite is CuFeS 2 , in which the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is as follows: The chalcopyrite is crushed and sieved to 150 μm, then it is subjected to ultrasonic treatment and pickling, and finally the treated chalcopyrite is stored in N 2In an atmosphere, take it out when in use.

[0104] This embodiment provides a sludge treatment method, adding the above-mentioned sludge dewatering agent to 490 g of sludge with a rotation speed of 300 rpm and stirring for 30 min. The pH value of the above-mentioned sludge is adjusted to 3.

[0105] Example 9

[0106] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0107] A sludge dewatering agent provided in this embodiment includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0108] The main component of the above-mentioned chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above-mentioned pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 In an atmosphere, take it out when in use.

[0109] This embodiment provides a sludge treatment method, adding the above-mentioned sludge dewatering agent to 488 g of sludge with a rotation speed of 280 pm and stirring for 30 min. The pH value of the above-mentioned sludge is adjusted to 3.

[0110] Example 10

[0111] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0112] A sludge dewatering agent provided in this embodiment includes 500 g of chalcopyrite and 18 g of sodium percarbonate.

[0113] The main component of the above-mentioned chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above-mentioned pretreatment is: crushing and sieving the chalcopyrite to 140 - 160 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 In an atmosphere, take it out when in use.

[0114] This embodiment provides a sludge treatment method, adding the above-mentioned sludge dewatering agent to 482 g of sludge with a rotation speed of 300 rpm and stirring for 30 min. The pH value of the above-mentioned sludge is adjusted to 3.

[0115] Example 11

[0116] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0117] A sludge dewatering treatment agent provided in this embodiment includes 500 g of chalcopyrite and 20 g of sodium percarbonate.

[0118] The main components of the above chalcopyrite are CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0119] This embodiment provides a sludge treatment method, adding the above sludge dewatering treatment agent to 480 g of sludge with a rotation speed of 300 rpm and stirring for 30 min. The pH value of the above sludge is adjusted to 3.

[0120] Example 12

[0121] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0122] A sludge dewatering treatment agent provided in this embodiment includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0123] The main components of the above chalcopyrite are CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0124] This embodiment provides a sludge treatment method, adding the above sludge dewatering treatment agent to 488 g of sludge with a rotation speed of 300 rpm and stirring for 30 min. The pH value of the above sludge is adjusted to 2.5.

[0125] Example 13

[0126] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0127] A sludge dewatering treatment agent provided in this embodiment includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0128] The main component of the above chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. Before use, the chalcopyrite is pre-treated. The above pre-treatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0129] This embodiment provides a sludge treatment method, adding the above sludge dewatering agent to 488 g of sludge with a rotation speed of 300 rpm and stirring for 30 min. The pH value of the above sludge is adjusted to 4.0.

[0130] Example 14

[0131] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0132] A sludge dewatering agent provided in this embodiment includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0133] The main component of the above chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. Before use, the chalcopyrite is pre-treated. The above pre-treatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0134] This embodiment provides a sludge treatment method, adding the above sludge dewatering agent to 488 g of sludge with a rotation speed of 300 rpm and stirring for 30 min. The pH value of the above sludge is adjusted to 5.0.

[0135] Example 15

[0136] This comparative example provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0137] A sludge dewatering agent provided in this comparative example includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0138] The main component of the above chalcopyrite is CuFeS 2, where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0139] This comparative example provides a sludge treatment method. Add the above sludge dewatering agent to 488 g of sludge with a rotation speed of 300 rpm and stir for 50 min. The pH value of the above sludge is adjusted to 6.0.

[0140] Example 16

[0141] This example provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0142] A sludge dewatering agent provided in this example includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0143] The main component of the above chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0144] This example provides a sludge treatment method. Add the above sludge dewatering agent to 488 g of sludge with a rotation speed of 300 rpm and stir for 20 min. The pH value of the above sludge is adjusted to 4.0.

[0145] Example 17

[0146] This example provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0147] A sludge dewatering agent provided in this example includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0148] The main component of the above chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2In an atmosphere, take it out when in use.

[0149] This embodiment provides a sludge treatment method. Add the above sludge dewatering agent to 488 g of sludge with a rotation speed of 300 rpm and stir for 40 min. Adjust the pH value of the above sludge to 4.0.

[0150] Example 18

[0151] This embodiment provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0152] A sludge dewatering agent provided in this embodiment includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0153] The main component of the above chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crush the chalcopyrite and screen it to 150 μm, then perform ultrasonic treatment and pickling on it, and finally store the treated chalcopyrite in N 2 In an atmosphere, take it out when in use.

[0154] This embodiment provides a sludge treatment method. Add the above sludge dewatering agent to 488 g of sludge with a rotation speed of 300 rpm and stir for 50 min. Adjust the pH value of the above sludge to 4.0.

[0155] Comparative Example 1

[0156] This comparative example provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0157] A sludge dewatering agent provided in this comparative example includes 15 g of sodium percarbonate.

[0158] This comparative example provides a sludge treatment method. Add the above sludge dewatering agent to 985 g of sludge with a rotation speed of 300 rpm and stir for 30 min. Adjust the pH value of the above sludge to 3.0.

[0159] Comparative Example 2

[0160] This comparative example provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0161] A sludge dewatering agent provided in this comparative example includes 500 g of chalcopyrite.

[0162] The main component of the above chalcopyrite is CuFeS 2, where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0163] This comparative example provides a sludge treatment method, adding the above sludge dewatering agent to 500 g of sludge with a rotation speed of 300 rpm and stirring for 50 min. The pH value of the above sludge is adjusted to 3.0.

[0164] Comparative Example 3

[0165] This comparative example provides a sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals and a sludge treatment method.

[0166] A sludge dewatering agent provided by this comparative example includes 500 g of chalcopyrite and 30 g of sodium percarbonate.

[0167] The main component of the above chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2 atmosphere and taking it out when in use.

[0168] This comparative example provides a sludge treatment method, adding the above sludge dewatering agent to 470 g of sludge with a rotation speed of 300 rpm and stirring for 30 min. The pH value of the above sludge is adjusted to 3.

[0169] Comparative Example 4

[0170] This comparative example provides a sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals and a sludge treatment method.

[0171] A sludge dewatering agent provided by this comparative example includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0172] The main component of the above chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crushing and sieving the chalcopyrite to 150 μm, then performing ultrasonic treatment and pickling on it, and finally storing the treated chalcopyrite in N 2In an atmosphere, take it out when in use.

[0173] This comparative example provides a sludge treatment method. Add the above sludge dewatering agent to 488 g of sludge with a rotation speed of 300 rpm and stir for 50 min. Adjust the pH value of the above sludge to 7.0.

[0174] Comparative Example 5

[0175] This comparative example provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0176] A sludge dewatering agent provided by this comparative example includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0177] The main component of the above chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crush the chalcopyrite and sieve it to 150 μm, then perform ultrasonic treatment and pickling on it, and finally store the treated chalcopyrite in N 2 In an atmosphere, take it out when in use.

[0178] This comparative example provides a sludge treatment method. Add the above sludge dewatering agent to 488 g of sludge with a rotation speed of 300 rpm and stir for 50 min. Adjust the pH value of the above sludge to 8.0.

[0179] Comparative Example 6

[0180] This comparative example provides a sludge dewatering agent and a sludge treatment method for heterogeneous catalytic oxidation of sulfide minerals.

[0181] A sludge dewatering agent provided by this comparative example includes 500 g of chalcopyrite and 12 g of sodium percarbonate.

[0182] The main component of the above chalcopyrite is CuFeS 2 , where the mass fraction of Cu is 33.22%, the mass fraction of Fe is 32.73%, and the mass fraction of S is 35.05%. The chalcopyrite is pretreated before use. The above pretreatment is: crush the chalcopyrite and sieve it to 150 μm, then perform ultrasonic treatment and pickling on it, and finally store the treated chalcopyrite in N 2 In an atmosphere, take it out when in use.

[0183] This comparative example provides a sludge treatment method. Add the above sludge dewatering agent to 488 g of sludge with a rotation speed of 300 rpm and stir for 10 min. Adjust the pH value of the above sludge to 4.0.

[0184] Test Example 1

[0185] The sludge treated in Examples 1-6 and Comparative Example 1 was collected, and the sludge resistance ratio (SRF) was measured respectively. The measurement results are as Figure 1 shown. It can be seen from this that as the dosage of chalcopyrite increased from 0 to 600 mg / g TS, the SRF gradually increased from 48.8% to 81.6%. This indicates that as the dosage of chalcopyrite increased, the dewaterability of the sludge improved. When the dosage of chalcopyrite was 500 mg / g TS, the SRF reached the best. When the dosage of chalcopyrite exceeded 500 mg / g TS, the dewatering performance of the sludge began to gradually decrease. This may be because too much chalcopyrite covered the active sites of sodium percarbonate.

[0186] Test Example 2

[0187] The sludge treated in Examples 5, 7-11 and Comparative Examples 2 and 3 was collected, and the sludge resistance ratio (SRF) was measured respectively. The measurement results are as Figure 2 shown. It can be seen from this that when the dosage of sodium percarbonate was 5-20 mg / g TS, the dewatering performance of the treated sludge was enhanced. When the dosage of sodium percarbonate was greater than 12 mg / g TS, the dewatering performance of the sludge gradually decreased. This is because when the dosage of sodium percarbonate is relatively large, it will induce -OH scavenging and react to occur in reactions (8) and (9), thus limiting the dewatering effect.

[0188] H 2 O 2 +·OH→H 2 O+·OOH (8)

[0189] ·OOH+·OH→H 2 O+O 2 (9)

[0190] Test Example 3

[0191] The sludge treated in Examples 12-15 and Comparative Examples 4 and 5 was collected, and the sludge resistance ratio (SRF) was measured respectively. The measurement results are as Figure 3 shown. It can be seen from this that when the pH value was 2.5-6, it was more conducive to the treatment of sludge by chalcopyrite and sodium percarbonate, and the dewatering rate of the sludge could be further enhanced. This is because the acidic environment not only facilitates the dissolution of Fe / Cu ions to generate reactive oxygen species, but also amplifies the oxidation efficiency of reactive oxygen species for EPS decomposition and the reduction of the ability to bind water. When the pH value was 3, the dewatering rate of the sludge treated by chalcopyrite and sodium percarbonate reached the best.

[0192] Test Example 4

[0193] The sludge treated in Examples 16-18 and Comparative Example 6 was collected, and the sludge resistance ratio (SRF) was measured respectively. The measurement results are asFigure 4 As shown, it can be seen that when the treatment time is 20 - 50 min, the dewatering performance of the sludge is better. If the time is too short or too long, the dewatering performance of the sludge is not good. When the treatment time is 30 min, the dewatering performance of the sludge reaches the best.

[0194] Test Example 5

[0195] Collect a part of the sludge treated in Example 13 and detect the content of triclocarban (TCC) in it. The specific detection method is as follows:

[0196] Prepare 1000 mL of 80 mg TCC / kg sludge; 1000 mL of 150 mg TCC / kg sludge; 1000 mL of 400 mg TCC / kg sludge respectively; add 10 mM of sodium azide to inhibit the microbial activity; adsorb in the dark at 120 rpm and 25 °C for 24 hours; then extract TCC from the dried sample by ultrasonic method + solid-phase extraction method, and determine the TCC concentration.

[0197] (2) Add 1M H2SO4 or NaOH solution to each sludge sample (300 mL) to adjust the pH value of the solution. Then, different doses of chalcopyrite and SPC are added to the sludge at a rotation speed of 300 rpm and reacted for 30 min. After the reaction, determine the TCC content in the sludge.

[0198] TCC extraction and extraction process: TCC in the sludge samples is all subjected to solid-phase extraction with an HLB (6 mL, 200 mg) column, and then passed through a 0.22 μm filter membrane to determine TCC. TCC in the sludge samples needs to be extracted first and then subjected to solid-phase extraction. The extraction steps are as follows: Take 10 mL of the sludge sample, place it in a -25 °C refrigerator and freeze for 48 h, and then freeze-dry for 36 h; take 0.1 g of the freeze-dried sludge sample, add 5 mL of methanol / acetone (95:5) mixed solution, react in a 100 Hz ultrasonic instrument for 30 min, and perform ultrasonic extraction three times in sequence. Obtain the extract by medium-speed centrifugation (centrifuge at 4000 rpm for 10 min).

[0199] TCC concentration test: Determine the TCC concentration by HPLC. The test conditions are: C18 chromatographic column (5.0 μm; 4.6 mm × 250 mm); the mobile phase is methanol and water (80:20); the flow rate is 0.6 mL / min; the injection volume is 50 μL; the column temperature is 30 °C; the detection wavelength is 280 nm.

[0200] The finally measured content of triclocarban in the sludge compared with the content of triclocarban in the untreated sludge is for reference Figure 5 , from which it can be seen that using chalcopyrite and sodium percarbonate as the sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals can also synergistically remove triclocarban.

[0201] Test Example 6

[0202] Collect a part of the sludge after the treatment in Example 13, and detect the content of resistance genes therein. The detected resistance genes are: sul1, sul2, tetQ, tetM-01, tetM-02, tetW, tetO-01, tetO-02, tetR, tetG, tetE. The specific detection method is as follows:

[0203] Add 1M H2SO4 or NaOH solution to each sludge sample (300 mL) to adjust the pH value of the solution. Then, add different doses of chalcopyrite and SPC to the sludge with a rotation speed of 300 rpm and react for 30 min. After the reaction, measure the content of ARGs in the sludge.

[0204] DNA extraction method:

[0205] The sludge DNA was extracted using a soil genomic DNA rapid extraction kit. The specific steps are as follows:

[0206] (1) Add 0.25 g of sludge sample, 750 μL of buffer SA, and 0.25 g of glass beads to a 2 mL centrifuge tube respectively, and vortex for 15 s.

[0207] (2) Add 60 μL of buffer SC to the sample, and vortex for 10 min until the sample is mixed evenly. After centrifuging at 12000 rpm / min for 1 min, transfer the supernatant (about 500 μL) to a new 2 mL centrifuge tube.

[0208] (3) Add 250 μL of buffer HA, vortex for 5 s, and then place it at 4 °C for 5 min. Then centrifuge at 12000 rpm / min for 1 min. Transfer the supernatant to a new 2 mL centrifuge tube.

[0209] (4) Add 200 μL of buffer HB and mix well. After placing it at 4 °C for 5 min, centrifuge at 12000 rpm / min for 1 min. Transfer the supernatant to a new 2 mL centrifuge tube, and add 1200 μL of buffer GF and invert to mix well. (Do not remove the precipitate when transferring the supernatant, otherwise the DNA purity may be reduced.)

[0210] (5) Take 700 μL of the solution obtained in the previous step and add it to an adsorption column CB3. Centrifuge at 12000 rpm / min for 30 s, pour out the waste liquid, and place the adsorption column CB3 in a centrifuge tube.

[0211] (6) Add 500 μL of washing solution PWS to the adsorption column CB3, centrifuge at 12000 rpm / min for 30 s, and pour out the supernatant.

[0212] (7) Add 500 μL of ethanol (70%) to adsorption column CB3, centrifuge at 12,000 rpm for 30 s, and pour off the supernatant.

[0213] (8) Place adsorption column CB3 at room temperature for several minutes to thoroughly dry the residual washing solution in the adsorption material. Transfer adsorption column CB3 into a clean 1.5 mL centrifuge tube, suspend and add 50 μL of ddH2O to the middle part of the adsorption membrane, place at room temperature for 3 min, then centrifuge at 12,000 rpm for 2 min. The solution in the obtained centrifuge tube is the purified DNA.

[0214] After DNA extraction, relevant detections of ARGs and microbial communities were carried out respectively.

[0215] Real-time fluorescence quantitative PCR:

[0216] The relevant detection of ARGs was entrusted to Shanghai Qiyin Biotechnology Company for detection. The specific steps are as follows: Use a SteponeplusTM Real-Time PCR instrument for PCR reaction. The reaction system is 5 μL of Roche Fast Start Universal SYBR Green Master solution, 0.4 μL of each forward primer and reverse primer, 1 μL of DNA template, 3 μL of sterilized water, and 0.2 μL of ROX Reference Dye. Adopt a two-step PCR amplification program. Reaction conditions: Pre-denaturation at 95 °C for 30 s; Denaturation at 95 °C for 5 s; Annealing and extension at 60 °C for 15 s (40 cycles).

[0217] The Ct value is the number of amplification cycles passed when the fluorescence signal of the amplification product reaches the set threshold during the PCR process. The Ct value measured after the reaction is used to calculate the absolute abundance and relative abundance of ARGs in each sample. The absolute abundance is measured by the standard curve method, and the relative abundance is the ratio of ARGs to 16S rRNA.

[0218] The content of resistance genes finally measured in the sludge compared with the content of resistance genes in the untreated sludge is referred to Figure 6 , from which it can be seen that using chalcopyrite and sodium percarbonate as sludge dehydrating agents for heterogeneous catalytic oxidation of sulfide minerals can also synergistically remove resistance genes.

[0219] In summary, a sludge dehydration treatment agent according to an embodiment of the present invention has at least the following beneficial effects:

[0220] Using chalcopyrite and sodium percarbonate as sludge dewatering agents for heterogeneous catalytic oxidation of sulfide minerals can effectively assist in sludge dewatering. The sludge treated with chalcopyrite and sodium percarbonate as sludge dewatering agents for heterogeneous catalytic oxidation of sulfide minerals shows a maximum dewatering rate that can reach 94.9%, the SRF can reach 0.96 ± 0.08 × 1012 m / kg, and the moisture content of the treated sludge cake is only 52.0 ± 0.9 wt%. While the dewatering rate of untreated sludge is only 51.3%, and it can be known from the experiment that the dewatering rate of sludge treated only with chalcopyrite is only 83.4%, and the dewatering rate of sludge treated only with sodium percarbonate is only 79.1%. The existing established α-Mn 2 O 3 + PMS treatment process for treating sludge, the moisture content of the sludge cake can only reach 71.8% at the lowest. The existing established iron-rich biochar + PMS treatment process for treating sludge, the moisture content of the sludge cake can only reach 58.9% at the lowest. While the moisture content of the sludge cake treated with chalcopyrite and sodium percarbonate as sludge dewatering agents for heterogeneous catalytic oxidation of sulfide minerals is only 52.0 ± 0.9 wt%.

[0221] Through research, it is found that chalcopyrite and sodium percarbonate can continuously generate a large amount of reactive oxygen through strong Fe and / or Cu cycles. The dominant reactive free radical ·OH and non-free radical 1 O 2 can effectively degrade macromolecular EPS into low-molecular biological polymers, reduce the secondary structure of highly polar hydrophilic proteins, and reduce the water-holding interface affinity. Then, the electrostatic force and interfacial free energy are reduced, enhancing the self-flocculation and fluidity, thereby promoting the reduction of bound water and the efficiency of mud-water separation.

[0222] In addition, it can be seen from Test Examples 5 and 6 that using this sludge dewatering agent for heterogeneous catalytic oxidation of sulfide minerals can also synergistically remove triclocarban and resistance genes, etc., assisting in further detoxifying the sludge and achieving unexpected effects in the original sludge treatment.

[0223] A sludge treatment method according to an embodiment of the present invention has at least the following beneficial effects:

[0224] The sludge resistance ratio (SRF) of the sludge treated in Examples 16-18 and Comparative Example 6 is as Figure 4 shown. From this, it can be seen that when the treatment time is 20-50 min, the dewatering performance of the sludge is better. If the time is too short or too long, the dewatering performance of the sludge is not good. When the treatment time is 30 min, the dewatering performance of the sludge reaches the best.

[0225] The embodiments described above are some, but not all, of the embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

Claims

1. Sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals, Characterized in that: It comprises chalcopyrite and sodium percarbonate, and the mass ratio of the chalcopyrite to the sodium percarbonate is 100 - 600∶5 - 20.

2. The sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals according to claim 1, Characterized in that: The mass ratio of the chalcopyrite to the sodium percarbonate is 200 - 500∶10 - 12.

3. The sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals according to claim 1, Characterized in that: The mass ratio of the chalcopyrite to the sodium percarbonate is 500∶12.

4. The sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals according to claim 1, Characterized in that: The chalcopyrite is pretreated before use, and the pretreatment is as follows: the chalcopyrite is crushed and screened to 140-160 μm, then it is subjected to ultrasonic treatment and pickling, and finally the treated chalcopyrite is stored in N 2 atmosphere.

5. Sludge treatment method, Characterized in that: The sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals described in any one of claims 1 - 4 is added to the sludge with a rotation speed of 280 - 320 rpm and stirred for 20 - 50 min to obtain the treated sludge.

6. The sludge treatment method according to claim 5, Characterized in that: The mass ratio of the dosage of the sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals to the sludge is 1∶2 - 10.

7. The sludge treatment method according to claim 5, Characterized in that: When the sludge is treated with the sludge dehydrating agent for heterogeneous catalytic oxidation of sulfide minerals, the pH value of the sludge is 2.5 - 6.

8. The sludge treatment method according to claim 7, Characterized in that: The pH value of the sludge is adjusted with sodium hydroxide solution or sulfuric acid solution.

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