A wastewater oxidation device and method

Abstract

A wastewater oxidation device and method. The device includes an influent regulation area for adjusting the pH of wastewater; a primary oxidation area for performing primary oxidation treatment on the wastewater output from the influent regulation area through an O3 / Fe 2+ / calcium peroxide / Oxone oxidation system; a secondary oxidation area for performing secondary oxidation treatment on the wastewater output from the primary oxidation area through an O3 / activated carbon / H2O2 / Oxone oxidation system; a tertiary oxidation area for performing tertiary oxidation treatment on the wastewater output from the secondary oxidation area through an O3 / ultraviolet light / persulfate / Oxone oxidation system. The present invention preferably solves the problem that a large amount of free radicals are generated in a short time but cannot be effectively utilized, and alleviates the contradiction between the transfer amount and the demand amount of free radicals. After the above treatment, the organic matter in the wastewater is efficiently degraded, and the biodegradability of the organic matter, especially the biodegradation rate of the organic matter, is significantly improved. The output wastewater is very suitable for further biochemical treatment.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and in particular, to a wastewater oxidation device and method. Background Art

[0002] Advanced oxidation is a commonly used water treatment technology and can be used as a pretreatment means before biochemical treatment. However, in the related technologies of advanced oxidation as a pretreatment means, the following problems still exist:

[0003] Most oxidants are added at a single point, resulting in a large amount of oxidants concentrating at one dosing point within a short time. A large amount of free radicals are generated within a short time, but it is difficult to efficiently mix and react with the organic matter in the surrounding wastewater. The contradiction between the transfer amount and the demand amount of free radicals is relatively prominent, and a large amount of free radicals are quickly quenched. Therefore, the utilization rate of the generated free radicals is relatively low.

[0004] The types and activation means of oxidants are single, resulting in low activation efficiency of oxidants, low utilization efficiency of oxidants, and insufficient generation amount of free radicals. In addition, traditional oxidants such as Fenton reagents produce a large amount of sludge during oxidation treatment and cause relatively serious secondary pollution.

[0005] The existence of the above problems makes the treatment efficiency of advanced oxidation as a pretreatment means insufficient. Specifically, the degradation efficiency of organic matter is low, the biodegradability of organic matter, especially the improvement of the biodegradation rate of organic matter, is insufficient, and the suitability of the oxidized effluent for further biochemical treatment is poor. Its use is greatly restricted, which is a difficult problem to be solved in the related technologies of advanced oxidation. Summary of the Invention

[0006] In view of this, the main purpose of the present invention is to provide a wastewater oxidation device and method, hoping to solve at least a part of the above-mentioned technical problems.

[0007] To achieve the above purpose, the technical solution of the present invention is as follows:

[0008] As one aspect of the present invention, a wastewater oxidation device is provided, including: an inlet adjustment area for adjusting the pH of wastewater; a primary oxidation area for passing through O3 / Fe 2+The wastewater output from the inlet water regulation area is subjected to primary oxidation treatment by a calcium peroxide / Oxone (i.e., potassium peroxymonosulfate compound salt) oxidation system; a secondary oxidation area is used to subject the wastewater output from the primary oxidation area to secondary oxidation treatment by an O3 / activated carbon (AC) / H2O2 / Oxone oxidation system; a tertiary oxidation area is used to subject the wastewater output from the secondary oxidation area to tertiary oxidation treatment by an O3 / ultraviolet light (UV) / persulfate (PDS) / Oxone oxidation system. After the above treatment, the organic matter in the wastewater is efficiently degraded, especially its biodegradability is significantly improved, and the output wastewater is very suitable for further biochemical treatment.

[0009] As another aspect of the present invention, a wastewater oxidation method using the wastewater oxidation device as described above is provided, including the following steps: adjusting the pH of the wastewater to be treated; subjecting the wastewater with adjusted pH to primary oxidation treatment by an O3 / Fe 2+ / calcium peroxide / Oxone oxidation system to obtain primary treated wastewater; subjecting the primary treated wastewater to secondary oxidation treatment by an O3 / activated carbon / H2O2 / Oxone oxidation system to obtain secondary treated wastewater; subjecting the secondary treated wastewater to tertiary oxidation treatment by an O3 / ultraviolet light / persulfate / Oxone oxidation system to obtain tertiary treated wastewater. After the above treatment, the organic matter in the wastewater is efficiently degraded, especially its biodegradability is significantly improved, and the output wastewater is very suitable for further biochemical treatment.

[0010] It can be seen from the above technical solutions that the wastewater oxidation device and method of the present invention have at least one or a part of the following beneficial effects:

[0011] In the present invention, the oxidant is added at multiple points to achieve multi-stage oxidation treatment, which is beneficial to solving the problem that a large amount of free radicals are generated in a short time but cannot be effectively utilized, and preferably solves the contradiction between the transfer amount and the demand amount of free radicals;

[0012] At the same time, different oxidation systems are optimally selected in each stage of the oxidation area. Through the combination of various oxidants and activation means, the generation of free radicals can be effectively promoted, so that each stage of the oxidation system is adapted to the water quality of the wastewater to be oxidized required at the corresponding stage, which is beneficial to improving the efficiency of wastewater oxidation treatment;

[0013] In the present invention, by adjusting the pH of the inlet water, hydrogen peroxide is slowly released from calcium peroxide during primary oxidation, overcoming the defect that liquid hydrogen peroxide decomposes too fast, improving the utilization rate of hydrogen peroxide, preferably solving the problem that a large amount of free radicals are generated in a short time but cannot be effectively utilized, and contributing to improving the efficiency of wastewater oxidation treatment;

[0014] After the wastewater is treated by oxidation according to the present invention, not only the degradation effect of organic matter and the improvement effect of BOD5 / COD are good, but also the biodegradation rate of organic matter is significantly enhanced, the biodegradation performance of organic matter is significantly improved, and the effluent is very conducive to further biochemical treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 is a side view structural diagram of the wastewater oxidation device according to an embodiment of the present invention;

[0016] Figure 2 is a schematic diagram of an integrated aeration and mechanical stirring structure according to an embodiment of the present invention;

[0017] Figure 3 is a flow chart of the wastewater oxidation method according to an embodiment of the present invention.

[0018] In the above-mentioned drawings, the meanings of the reference numerals are specifically as follows:

[0019] 100, wastewater oxidation device;

[0020] 101, device wall; 102 - water passing orifice plate I;

[0021] 103 - water passing orifice plate II;

[0022] 200, inlet adjustment area;

[0023] 201, inlet system; 202, acid-base solution dosing system;

[0024] 203, mechanical stirring system;

[0025] 300, primary oxidation area;

[0026] 310, primary rapid mixing reaction area;

[0027] 311, ozone dosing and mechanical stirring system; 312, Oxone dosing system;

[0028] 313, Fe 2+ dosing system; 314, calcium peroxide dosing system; 320, primary slow mixing reaction area;

[0029] 321, mechanical stirring system;

[0030] 400, secondary oxidation area;

[0031] 410, secondary rapid mixing reaction area;

[0032] 411, ozone dosing and mechanical stirring system; 412, Oxone dosing system;

[0033] 413, activated carbon dosing system; 414, H2O2 dosing system;

[0034] 420. Secondary slow mixing and reaction zone;

[0035] 421. Mechanical stirring system;

[0036] 500. Tertiary oxidation zone;

[0037] 510. Tertiary rapid mixing and reaction zone;

[0038] 511. Ozone dosing and mechanical stirring system; 512. Oxone dosing system;

[0039] 513. Ultraviolet light system; 514. Persulfate dosing system 520. Tertiary slow mixing and reaction zone;

[0040] 521. Mechanical stirring system;

[0041] 600. Residual oxidation species elimination zone;

[0042] 601. Reducing agent dosing system; 602. Mechanical stirring system;

[0043] 700. Adjusting effluent zone;

[0044] 710. pH adjustment zone;

[0045] 711. Acid-base solution dosing system; 712. Mechanical stirring system;

[0046] 720. Effluent zone;

[0047] 721. Effluent system;

[0048] 800. Integrated aeration and mechanical stirring structure;

[0049] 801. Mechanical stirring shaft; 802. Ozone generator outlet pipe;

[0050] 803. Multifunctional valve; 804. Ozone main pipe;

[0051] 805. Ozone branch pipe; 806. Aeration rod;

[0052] 807. Aeration disc; 808. Stirring blade. Detailed implementation manners

[0053] To make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to specific embodiments and the accompanying drawings.

[0054] In the process of implementing the present invention, it is found that in the related technologies of wastewater oxidation, there are problems such as single types of oxidants, dosing methods, and activation means, which cannot fully utilize the large amount of free radicals generated in a short time, making it difficult to effectively degrade the organic matter in wastewater, thus restricting the application of wastewater oxidation treatment. Further, the present invention provides a wastewater oxidation device and method, which solve the defect of insufficient generation of free radicals through the combination of multiple oxidants and multiple activation means, and achieve multi-stage oxidation by dosing oxidants at multiple points to solve the problem that a large amount of free radicals are generated in a short time but cannot be effectively utilized, improving the utilization efficiency of the oxidation system and the transfer efficiency of free radicals, thereby improving the oxidation treatment efficiency and significantly enhancing the degradation efficiency of organic matter in wastewater and its biodegradability.

[0055] Specifically, according to some embodiments of the present invention, a wastewater oxidation device is provided. Figure 1 is a side view structural diagram of the wastewater oxidation device according to an embodiment of the present invention, as Figure 1 shown, the wastewater oxidation device 100 mainly includes: an influent regulation area 200, a primary oxidation area 300, a secondary oxidation area 400, and a tertiary oxidation area 500. Among them, the influent regulation area 200 is used to adjust the pH of the wastewater; the primary oxidation area 300 is used to perform primary oxidation treatment on the wastewater output from the influent regulation area 200 through an O3 / Fe 2+ / calcium peroxide / Oxone (i.e., potassium peroxymonosulfate compound salt) oxidation system; the secondary oxidation area 400 is used to perform secondary oxidation treatment on the wastewater output from the primary oxidation area 300 through an O3 / activated carbon / H2O2 / Oxone oxidation system; the tertiary oxidation area 500 is used to perform tertiary oxidation treatment on the wastewater output from the secondary oxidation area 400 through an O3 / ultraviolet light / persulfate / Oxone oxidation system. After the above treatment, the organic matter in the wastewater is efficiently degraded, especially its biodegradability is significantly improved, and the output wastewater is very suitable for further biochemical treatment.

[0056] According to the embodiments of the present invention, by adjusting the influent pH, calcium peroxide slowly releases hydrogen peroxide in the primary oxidation, overcoming the defect of too fast decomposition of liquid hydrogen peroxide, which can improve the utilization rate and activation efficiency of the oxidant; using activated carbon, etc. to promote the generation of free radicals in the secondary oxidation system, further effectively degrading the residual organic matter, and the COD and chromaticity of the wastewater are further significantly reduced; for low-chromaticity wastewater, activation methods such as ultraviolet light can be fully utilized to promote the generation of free radicals by oxidants in the tertiary oxidation system. Thus, by dosing oxidants at multiple points and optimizing the oxidation systems at all levels, the utilization efficiency of the oxidation system and the transfer efficiency of free radicals are improved, thereby improving the oxidation treatment efficiency and significantly enhancing the degradation efficiency of organic matter in wastewater and its biodegradability.

[0057] According to the embodiments of the present invention, asFigure 1 As shown, the wastewater oxidation device 100 is of a vertical structure. The influent regulation area 200, the primary oxidation area 300, the secondary oxidation area 400, and the tertiary oxidation area 500 are sequentially arranged in the wastewater oxidation device 100 from bottom to top. However, it is not limited to this. The wastewater oxidation device 100 can also be of a horizontal structure, but the floor area is relatively larger than that of the vertical structure. At this time, the influent regulation area 200, the primary oxidation area 300, the secondary oxidation area 400, and the tertiary oxidation area 500 can be sequentially arranged in the wastewater oxidation device along the horizontal direction, as long as it is consistent with the direction of wastewater transmission.

[0058] According to an embodiment of the present invention, as Figure 1 shown, the wastewater oxidation device 100 includes a device wall 101 and a plurality of water-passing orifice plates I 102. The device wall 101 is used to form a wastewater treatment area; the plurality of water-passing orifice plates I 102 are used to divide the wastewater treatment area to form the influent regulation area 200, the primary oxidation area 300, the secondary oxidation area 400, and the tertiary oxidation area 500. The separation setting of the water-passing orifice plates I 102 simplifies the device structure.

[0059] According to an embodiment of the present invention, more specifically, the influent regulation area 200 is equipped with an influent system 201, an acid-base solution dosing system 202, and a mechanical stirring system 203. The influent system 201 is used to input wastewater into the influent regulation area 200; the acid-base solution dosing system 202 is used to dose acid-base solution into the wastewater in the influent regulation area 200; the mechanical stirring system 203 is used to mix the acid-base solution and the wastewater to adjust the pH of the wastewater.

[0060] Preferably, the pH of the wastewater in the influent regulation area 200 can be adjusted to 5.7 - 6.3, which is beneficial to controlling the rate of hydrogen peroxide release from calcium peroxide, overcomes the defect of too fast decomposition of liquid hydrogen peroxide, and improves the utilization efficiency of hydrogen peroxide.

[0061] According to an embodiment of the present invention, the primary oxidation area 300 includes a primary rapid mixing reaction area 310 and a primary slow mixing reaction area 320. The primary rapid mixing reaction area 310 is used to rapidly mix the wastewater output from the influent regulation area 200 with the O3 / Fe 2+ / calcium peroxide / Oxone oxidation system and carry out an oxidation reaction; the primary slow mixing reaction area 320 is used to make the wastewater output from the primary rapid mixing reaction area 310 continue to carry out an oxidation reaction to complete the primary oxidation treatment.

[0062] According to an embodiment of the present invention, further optionally, the primary rapid mixing reaction area 310 is equipped with an ozone dosing and mechanical stirring system 311, an Oxone dosing system 312, Fe 2+A dosing system 313 and a calcium peroxide dosing system 314; a mechanical stirring system 321 is installed in the first-stage slow mixing reaction zone 320.

[0063] According to an embodiment of the present invention, further optionally, the first-stage rapid mixing reaction zone 310 and the first-stage slow mixing reaction zone 320 are separated by a water passing orifice plate II 103, and the hydraulic retention time ratio between the first-stage rapid mixing reaction zone 310 and the first-stage slow mixing reaction zone 320 is 1:6 to 1:8.

[0064] According to an embodiment of the present invention, the secondary oxidation zone 400 includes a secondary rapid mixing reaction zone 410 and a secondary slow mixing reaction zone 420. The secondary rapid mixing reaction zone 410 is used to rapidly mix the wastewater output from the primary oxidation zone 300 with the O3 / activated carbon / H2O2 / Oxone oxidation system and carry out an oxidation reaction; the secondary slow mixing reaction zone 420 is used to make the wastewater output from the secondary rapid mixing reaction zone 410 continue to carry out an oxidation reaction to complete the secondary oxidation treatment.

[0065] According to an embodiment of the present invention, further optionally, an ozone dosing and mechanical stirring system 411, an Oxone dosing system 412, an activated carbon dosing system 413, and an H2O2 dosing system 414 are installed in the secondary rapid mixing reaction zone 410; a mechanical stirring system 421 is installed in the secondary slow mixing reaction zone 420.

[0066] According to an embodiment of the present invention, further optionally, the secondary rapid mixing reaction zone 410 and the secondary slow mixing reaction zone 420 are separated by a water passing orifice plate II 103, and the hydraulic retention time ratio between the secondary rapid mixing reaction zone 410 and the secondary slow mixing reaction zone 420 is 1:3 to 1:5.

[0067] According to an embodiment of the present invention, the tertiary oxidation zone 500 includes a tertiary rapid mixing reaction zone 510 and a tertiary slow mixing reaction zone 520. The tertiary rapid mixing reaction zone 510 is used to rapidly mix the wastewater output from the secondary oxidation zone 400 with the O3 / ultraviolet light / persulfate / Oxone oxidation system and carry out an oxidation reaction; the tertiary slow mixing reaction zone 520 is used to make the wastewater output from the tertiary rapid mixing reaction zone 510 continue to carry out an oxidation reaction to complete the tertiary oxidation treatment.

[0068] According to an embodiment of the present invention, an ozone dosing and mechanical stirring system 511, an Oxone dosing system 512, an ultraviolet light system 513, and a persulfate dosing system 514 are installed in the tertiary rapid mixing reaction zone 510; a mechanical stirring system 521 is installed in the tertiary slow mixing reaction zone 520. More specifically, the persulfate (PDS) dosed by the persulfate dosing system 514 can be sodium persulfate used in the embodiments of the present invention, but is not limited thereto.

[0069] According to an embodiment of the present invention, the three - stage rapid mixing reaction zone 510 and the three - stage slow mixing reaction zone 520 are separated by a water - passing orifice plate II 103, and the hydraulic retention time ratio between the three - stage rapid mixing reaction zone 510 and the three - stage slow mixing reaction zone 520 is 1:4 to 1:6.

[0070] According to an embodiment of the present invention, the ozone dosing and mechanical stirring systems 311, 411, 511 adopt an integrated aeration and mechanical stirring structure 800. Figure 2 is a schematic diagram of the integrated aeration and mechanical stirring structure of the embodiment of the present invention, as Figure 2 shown, the integrated aeration and mechanical stirring structure 800 includes a mechanical stirring shaft 801, an ozone generator outlet pipe 802, a multi - function valve 803, an ozone main pipe 804, ozone branch pipes 805, aeration rods 806, aeration discs 807, and stirring blades 808, all of which can adopt conventional structures in the art.

[0071] Among them, the mechanical stirring shaft 801 is used for rotating driven by a motor; the ozone generator outlet pipe 802 is used for gas transmission at the outlet of the ozone generator; the multi - function valve 803 movably connects the mechanical stirring shaft 801 and the ozone generator outlet pipe 802 together; the ozone main pipe 804 is connected to the multi - function valve 803 and rotates driven by the mechanical stirring shaft 801; multiple ozone branch pipes 805 are respectively communicated with the ozone main pipe 804 and extend along the axial direction parallel to the mechanical stirring shaft 801; multiple aeration rods 806 are respectively arranged at the ends of the multiple ozone branch pipes 805 and are communicated with the ozone branch pipes 805; multiple aeration discs 807 are respectively vertically arranged at the ends of the multiple aeration rods 806 and are communicated with the aeration rods 806; the stirring blades 808 are fixed on the ozone branch pipes 805 and extend along the direction perpendicular to the ozone branch pipes 805.

[0072] According to an embodiment of the present invention, the multi - function valve 803 can adopt a commonly used rotary joint in the art, so as to realize the transmission of ozone from the static outlet of the ozone generator to the dynamically rotating ozone main pipe. As Figure 2 shown in, it is preferably to adopt a combination of the aeration rod 806 and the aeration disc 807 for aeration, wherein the aeration rod 806 is arranged at the end of the ozone branch pipe 805, and the aeration disc 807 is arranged at the end of the aeration rod 806, so as to facilitate the large - amount release of ozone.

[0073] According to an embodiment of the present invention, the ozone dosing and mechanical stirring systems 311, 411, 511 can also adopt a structure in which the ozone dosing system and the mechanical stirring system are separately arranged. However, compared with this separately arranged structure, the integrated aeration and mechanical stirring structure 800 of the present invention lies in that the aeration rods 806 and the aeration discs 807 are in a rotating state, which will enhance the shear mixing ability on the horizontal and vertical planes, thereby helping to improve the oxidant transportation, mixing and utilization efficiency and the free radical transportation and transfer efficiency, and further improving the wastewater oxidation treatment efficiency.

[0074] According to an embodiment of the present invention, in order to make the effluent of the wastewater oxidation device 100 suitable for use as the wastewater for biochemical treatment, the wastewater oxidation device 100 further includes: a residual oxidation species elimination area 600 and an effluent adjustment area 700. The residual oxidation species elimination area 600 is used to reduce the wastewater output from the tertiary oxidation area 500 through a reduction system to remove the residual oxides in the wastewater; and the effluent adjustment area 700 is used to adjust the pH of the wastewater output from the residual oxidation species elimination area 600 and output the wastewater suitable for biochemical treatment.

[0075] According to an embodiment of the present invention, further optionally, the residual oxidation species elimination area 600 and the effluent adjustment area 700 are also separated and formed in the wastewater treatment area by the porous partition plate I 102. The separation setting through the water-permeable plate I 102 simplifies the device structure.

[0076] According to an embodiment of the present invention, a reductant dosing system 601 and a mechanical stirring system 602 are installed in the residual oxidation species elimination area 600. Among them, the reductant dosing system 601 is used to dose a reductant such as sodium sulfite into the wastewater in the residual oxidation species elimination area 600 to eliminate the residual oxidation species in the wastewater; the mechanical stirring system 602 is used to mix the reductant and the wastewater to perform reduction treatment on the wastewater.

[0077] According to an embodiment of the present invention, the total hydraulic retention time of the primary oxidation area 300, the secondary oxidation area 400, the tertiary oxidation area 500 and the residual oxidation species elimination area 600 is preferably 60 - 80 minutes, and the hydraulic retention time ratio is preferably (7 - 9):(4 - 6):(5 - 7):1.

[0078] According to an embodiment of the present invention, the effluent adjustment area 700 includes a pH adjustment area 710 and an effluent area 720. The pH adjustment area 710 is used to adjust the pH of the wastewater output from the residual oxidation species elimination area 600, and the effluent area 720 is used to output the wastewater adjusted by the pH adjustment area 710, for example, it can be output to the biochemical treatment unit.

[0079] According to an embodiment of the present invention, an acid-base solution dosing system 711 and a mechanical stirring system 712 are installed in the pH adjustment zone 710. The acid-base solution dosing system 711 is used to dose acid-base solution into the wastewater in the pH adjustment zone 710; the mechanical stirring system 712 is used to mix the acid-base solution and the wastewater to adjust the pH of the wastewater. Preferably, the pH of the wastewater in the pH adjustment zone can be adjusted to 7.2 - 7.4 to meet the pH range requirements of biochemical treatment mainly based on microorganisms.

[0080] According to an embodiment of the present invention, an effluent system 721 is installed in the effluent zone 720, which is used to continue the reaction of the wastewater output from the pH adjustment zone 710 and output it after the pH adjustment is completed, for example, it can be output to a biochemical treatment unit.

[0081] According to an embodiment of the present invention, the hydraulic retention times of the influent adjustment zone 200, the pH adjustment zone 710, and the effluent zone 720 are 9 - 11 min, 3 - 5 min, and 5 - 7 min respectively.

[0082] According to an embodiment of the present invention, the stirring speeds of the mechanical stirring systems 203, 602, and 712 are 120 - 140 r / min, for example, they can be 120 r / min, 130 r / min, 140 r / min, etc.; the stirring speeds of the ozone dosing and mechanical stirring systems 311, 411, and 511 are 260 - 280 r / min, for example, they can be 260 r / min, 270 r / min, 280 r / min, etc.; the stirring speeds of the mechanical stirring systems 321, 421, and 521 are 70 - 90 r / min, for example, they can be 70 r / min, 80 r / min, 90 r / min, etc.

[0083] According to some embodiments of the present invention, a wastewater oxidation method using the wastewater oxidation device as described above is also provided. Figure 3 is a flowchart of the wastewater oxidation method according to an embodiment of the present invention, as Figure 3 shown, this wastewater oxidation method mainly includes the following steps:

[0084] Step S1: Adjust the pH of the wastewater to be treated. Preferably, the pH of the wastewater to be treated is adjusted to 5.7 - 6.3.

[0085] Step S2: Perform primary oxidation treatment on the pH-adjusted wastewater through the O3 / Fe 2+ / calcium peroxide / Oxone oxidation system to obtain primary treated wastewater;

[0086] Step S3: Perform secondary oxidation treatment on the primary treated wastewater through the O3 / activated carbon / H2O2 / Oxone oxidation system to obtain secondary treated wastewater;

[0087] Step S4: The secondary treated wastewater is subjected to tertiary oxidation treatment through an O3 / ultraviolet light / persulfate / Oxone oxidation system to obtain tertiary treated wastewater. Through the above treatment, the organic matter in the wastewater is efficiently degraded, especially its biodegradability is significantly improved, and the output wastewater is very suitable for further biochemical treatment.

[0088] According to an embodiment of the present invention, the O3 / Fe 2+ / calcium peroxide / Oxone oxidation system includes: 4 - 6 mg / L of O3, 19 - 21 mg / L of Fe 2+ , 24 - 26 mg / L of calcium peroxide and 16 - 18 mg / L of Oxone; by optimizing the dosage of the medicaments in the primary oxidation system to the appropriate range, it is beneficial to improve the efficiency of the primary oxidation treatment.

[0089] According to an embodiment of the present invention, the O3 / activated carbon / H2O2 / Oxone oxidation system includes: 5 - 7 mg / L of O3, 12 - 14 mg / L of activated carbon, 0.12 - 0.13 ml / L of 30 wt% H2O2 and 15 - 17 mg / L of Oxone; by optimizing the dosage of the medicaments in the secondary oxidation system to the appropriate range, it is beneficial to improve the efficiency of the secondary oxidation treatment.

[0090] According to an embodiment of the present invention, the O3 / ultraviolet light / persulfate / Oxone oxidation system includes: ultraviolet light with a wavelength of 240 - 260 nm and a power of 5 - 8 W, 6 - 8 mg / L of O3, 16 - 18 mg / L of persulfate and 14 - 16 mg / L of Oxone. By optimizing the dosage of the medicaments and the ultraviolet light conditions in the tertiary oxidation system to the appropriate range, it is beneficial to improve the efficiency of the tertiary oxidation treatment.

[0091] According to an embodiment of the present invention, the wastewater oxidation method of the present invention further includes: after performing reduction treatment and pH adjustment on the tertiary treated wastewater, outputting wastewater suitable for biochemical treatment. More specifically, sodium sulfite can be used as a reducing agent to perform reduction treatment on the wastewater, and the dosage of the 5.0 mM sodium sulfite solution is 1.0 - 1.2 ml / L. More specifically, the pH of the tertiary treated wastewater is preferably adjusted to 7.2 - 7.4.

[0092] According to an embodiment of the present invention, the wastewater oxidation device and method of the present invention are particularly suitable for treating the biochemical effluent of traditional Chinese medicine preparation wastewater, with a COD of 380 - 400 mg / L, a chromaticity of 95 - 115 times, a pH of 6 - 9, a BOD5 / COD of 0.08 - 0.11, and a biodegradation rate of 0.12 - 0.14 d -1 .

[0093] The technical solution of the present invention will be further elaborated and explained through specific embodiments below. It should be noted that the following specific embodiments are only for illustrative purposes and are not used to limit the present invention. The experimental methods used in the following embodiments are conventional methods unless otherwise specified; the wastewater to be treated is the biochemical effluent taken from a traditional Chinese medicine preparation enterprise (COD is 395 mg / L, chromaticity is 113 times, pH is 7.6, BOD5 / COD is 0.09, and the biodegradation rate is 0.12 d -1 ), and the materials, reagents, instruments, etc. used are all commercially available unless otherwise specified.

[0094] Example 1: Establishment of the type of oxidation system

[0095] Example 1-1:

[0096] Adopt the wastewater oxidation device 100 as Figure 1 shown. The wastewater enters the influent regulation area 200 from the bottom of the device and stays for 10 minutes. During this period, the pH of the wastewater is adjusted to 6.0 with dilute sulfuric acid at a state of 130 r / min.

[0097] The above effluent then enters the primary rapid mixing reaction area 310 and the primary slow mixing reaction area 320 of the primary oxidation area 300 in sequence. In the primary rapid mixing reaction area 310, O3, Fe 2+ , calcium peroxide, and Oxone (the dosing amounts are 5 mg / L, 20 mg / L, 25 mg / L, and 17 mg / L respectively) are added to the wastewater simultaneously for 4 minutes of oxidation treatment, and the stirring speed during the reaction process is 270 r / min. In the primary slow mixing reaction area 320, 28 minutes of oxidation treatment is carried out, and the stirring speed during the reaction process is 80 r / min.

[0098] The effluent of the primary oxidation area 300 then enters the secondary rapid mixing reaction area 410 and the secondary slow mixing reaction area 420 of the secondary oxidation area 400 in sequence. In the secondary rapid mixing reaction area 410, O3, activated carbon, 30 wt% H2O2, and Oxone (the dosing amounts are 6 mg / L, 13 mg / L, 0.13 ml / L, and 16 mg / L respectively) are added to the wastewater simultaneously for 4 minutes of oxidation treatment, and the stirring speed during the reaction process is 270 r / min. In the secondary slow mixing reaction area 420, 16 minutes of oxidation treatment is carried out, and the stirring speed during the reaction process is 80 r / min.

[0099] The effluent of the secondary oxidation zone 400 then successively enters the tertiary rapid mixing reaction zone 510 and the tertiary slow mixing reaction zone 520 of the tertiary oxidation zone 500. In the tertiary rapid mixing reaction zone 510, first turn on the ultraviolet light (UV, 250 nm, 5 W) lamp tubes, and then simultaneously add O3, sodium persulfate (commonly used PDS), and Oxone (the dosing amounts are 7 mg / L, 17 mg / L, and 15 mg / L respectively) to the influent for 4 minutes of oxidation treatment. The stirring speed during the reaction process is 270 r / min. In the tertiary slow mixing reaction zone 520, carry out 20 minutes of oxidation treatment, and the stirring speed during the reaction process is 80 r / min.

[0100] The effluent of the tertiary oxidation zone 500 then enters the residual oxidation species elimination zone 600, and add a 5.0 mM sodium sulfite solution (the dosing amount is 1.1 ml / L) to the wastewater for 4 minutes of reduction reaction. The stirring speed during the reaction process is 130 r / min.

[0101] The effluent of the residual oxidation species elimination zone 600 then enters the pH adjustment zone 710 and the effluent zone 720 of the effluent adjustment zone 700. Add NaOH solution to the wastewater for 4 minutes of mixing, and the stirring speed during the mixing process is 130 r / min; the effluent of the pH adjustment zone 710 enters the effluent zone 720, and the wastewater stays in the effluent zone 720 for 6 minutes and is discharged when the pH of the wastewater is adjusted to 7.2.

[0102] Separate the water samples of the influent, the effluent of the primary oxidation zone 300, the effluent of the secondary oxidation zone 400, and the effluent of the tertiary oxidation zone 500 and let them stand for 30 minutes respectively. Take the supernatant for index analysis, and the results are shown in Table 1 below:

[0103] Table 1

[0104]

[0105] As can be seen from the results in Table 1 above, in the effluent after the oxidation treatment in the primary oxidation zone 300, the secondary oxidation zone 400, and the tertiary oxidation zone 500, not only the COD and chromaticity are significantly reduced, achieving good organic matter degradation effects, but also the BOD5 / COD and the biodegradation rate constant are significantly increased, indicating that the biodegradation performance of organic matter is significantly improved. Especially after the treatment by the tertiary oxidation system in the tertiary oxidation zone 500, the biodegradation rate constant of its effluent increases by 115% compared with the effluent of the secondary oxidation zone. The promotion of the organic biodegradation rate by the tertiary oxidation system is particularly significant.

[0106] Example 1-2

[0107] Similar to the operation of Example 1-1, the main difference lies in adjusting the type of the primary oxidation system. The water samples of the influent and the effluent from the primary oxidation zone are allowed to stand for 30 minutes, and the supernatant is taken for index analysis. The results are shown in Table 2 below:

[0108] Table 2

[0109]

[0110] As can be seen from the results in Table 2 above, adding calcium peroxide and Fe 2+ in the primary oxidation system helps to improve the degradation effect of organic matter and the biodegradability performance.

[0111] Example 1-3

[0112] Similar to the operation of Example 1-1, the main difference lies in adjusting the type of the secondary oxidation system. The water samples of the influent and the effluent from the secondary oxidation zone are allowed to stand for 30 minutes, and the supernatant is taken for index analysis. The results are shown in Table 3 below:

[0113] Table 3

[0114]

[0115] As can be seen from the results in Table 3 above, the secondary oxidation system realizes the efficient oxidation treatment of the wastewater in the secondary oxidation zone, and the biodegradability performance of the organic matter is improved to a certain extent.

[0116] Example 1-4

[0117] Similar to the operation of Example 1-1, the main difference lies in adjusting the type of the tertiary oxidation system. The water samples of the influent and the effluent from the tertiary oxidation zone are allowed to stand for 30 minutes, and the supernatant is taken for index analysis. The results are shown in Table 4 below:

[0118] Table 4

[0119] As can be seen from the results in Table 4 above, activation means such as UV helps to generate a large amount of free radicals, thereby improving the oxidation treatment effect of the wastewater in the tertiary oxidation zone; PDS and Oxone are two different oxidants, and adding both of them simultaneously in the O3 / UV / PDS / Oxone system significantly improves the oxidation treatment effect and also significantly improves the biodegradation rate.

[0120] Example 2: Establishment of the tertiary oxidation system

[0121] Example 2-1

[0122] The operation is similar to that of Example 1-1, except that the order of the oxidation systems at each stage is adjusted, where O3 / Fe 2+ / calcium peroxide / Oxone, O3 / activated carbon / H2O2 / Oxone, and O3 / UV / PDS / Oxone are denoted as oxidation systems A, B, and C in sequence. The water samples of the influent and the effluent from the three-stage oxidation zone are each allowed to stand for 30 minutes, and the supernatant is taken for index analysis. The results are shown in Table 5 below:

[0123] Table 5

[0124] As can be seen from the results in Table 5 above, the setting of the order of the oxidation systems at each stage has a greater impact on the oxidation treatment effect of the wastewater. Especially when the O3 / UV / PDS / Oxone oxidation system is used as the oxidation system in the primary oxidation zone, it is particularly unfavorable for improving the oxidation effect of the wastewater.

[0125] Example 2-2

[0126] The operation is similar to that of Example 1-1, except that the oxidation systems at each stage are adjusted to the same oxidation system, denoted in the form of, for example, A→A→A. The water samples of the influent and the effluent from the three-stage oxidation zone are each allowed to stand for 30 minutes, and the supernatant is taken for index analysis.

[0127] Or the same oxidation system is added in the primary oxidation zone according to the total dosage for the three stages, denoted in the form of, for example, A+A+A. The water samples of the influent and the effluent from the primary oxidation zone are each allowed to stand for 30 minutes, and the supernatant is taken for index analysis. The results are shown in Table 6 below:

[0128] Table 6

[0129] As can be seen from the results in Table 6 above, adopting the multi-point dosing method of the oxidation system is more beneficial for improving the oxidation effect of the wastewater and the biodegradability of organic matter compared to the method of dosing with the same total dosage of drugs at a single point; and, adopting different oxidation systems in each stage of the oxidation zone is also more beneficial for improving the oxidation effect of the wastewater and the biodegradability of organic matter compared to adopting a single oxidation system;

[0130] The specific embodiments described above further illustrate the object, technical solution, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A wastewater oxidation device, comprising: An influent regulation zone for adjusting the pH of the wastewater; The primary oxidation zone is used to perform primary oxidation treatment on the wastewater output from the influent regulation zone through the O3 / Fe 2+ / calcium peroxide / Oxone oxidation system; A secondary oxidation zone for performing secondary oxidation treatment on the wastewater output from the primary oxidation zone through an O3 / activated carbon / H2O2 / Oxone oxidation system; A tertiary oxidation zone for performing tertiary oxidation treatment on the wastewater output from the secondary oxidation zone through an O3 / ultraviolet light / persulfate / Oxone oxidation system; after the tertiary oxidation treatment, the output wastewater is suitable for further biochemical treatment; And A residual oxidant species elimination zone for performing reduction treatment on the wastewater output from the tertiary oxidation zone through a reduction system to remove the residual oxidant species in the wastewater; The hydraulic retention time ratio of the primary oxidation zone, the secondary oxidation zone, the tertiary oxidation zone, and the residual oxidant species elimination zone is (7-9):(4-6):(5-7):

1.

2. The wastewater oxidation device according to claim 1, wherein, The device comprises: A device wall for forming a wastewater treatment area; and A plurality of water passing orifice plates I for partitioning the wastewater treatment area to form the influent regulation zone, the primary oxidation zone, the secondary oxidation zone, and the tertiary oxidation zone.

3. The wastewater oxidation device according to claim 1, wherein, The primary oxidation zone comprises: The first-stage rapid mixing and reaction zone is equipped with an ozone dosing and mechanical stirring system, an Oxone dosing system, an Fe 2+ dosing system, and a calcium peroxide dosing system; and A primary slow mixing reaction zone equipped with a mechanical stirring system; Wherein, the primary fast mixing reaction zone and the primary slow mixing reaction zone are separated by a water passing orifice plate II, and the hydraulic retention time ratio between the primary fast mixing reaction zone and the primary slow mixing reaction zone is 1:6-1:

8.

4. The wastewater oxidation device according to claim 1, wherein, The secondary oxidation zone comprises: A secondary fast mixing reaction zone equipped with an ozone dosing and mechanical stirring system, an Oxone dosing system, an activated carbon dosing system, and an H2O2 dosing system; and A secondary slow mixing reaction zone equipped with a mechanical stirring system; Wherein, the secondary fast mixing reaction zone and the secondary slow mixing reaction zone are separated by a water passing orifice plate II, and the hydraulic retention time ratio between the secondary fast mixing reaction zone and the secondary slow mixing reaction zone is 1:3-1:

5.

5. The wastewater oxidation device according to claim 1, wherein, The tertiary oxidation zone comprises: A tertiary fast mixing reaction zone equipped with an ozone dosing and mechanical stirring system, an Oxone dosing system, an ultraviolet light system, and a persulfate dosing system; and A tertiary slow mixing reaction zone equipped with a mechanical stirring system; Wherein, the tertiary fast mixing reaction zone and the tertiary slow mixing reaction zone are separated by a water passing orifice plate II, and the hydraulic retention time ratio between the tertiary fast mixing reaction zone and the tertiary slow mixing reaction zone is 1:4-1:

6.

6. The wastewater oxidation device according to any one of claims 3 to 5, wherein, The ozone dosing and mechanical stirring system comprises: A mechanical stirring shaft for rotating driven by a motor; An ozone generator outlet pipe for conveying the gas from the outlet of the ozone generator; A multi-functional valve for movably connecting the mechanical stirring shaft and the ozone generator outlet pipe, and the multi-functional valve is communicated with the ozone generator outlet pipe; An ozone main pipe communicated with the multi-functional valve and rotating driven by the mechanical stirring shaft; A plurality of ozone branch pipes respectively communicated with the ozone main pipe and extending along the axial direction parallel to the mechanical stirring shaft; Multiple aeration rods are respectively arranged at the ends of multiple ozone gas branch pipes and are communicated with the ozone gas branch pipes; Multiple aeration discs are respectively vertically arranged at the ends of the aeration rods and are communicated with the aeration rods; Stirring blades are fixed on multiple ozone gas branch pipes and extend in a direction perpendicular to the ozone gas branch pipes.

7. The wastewater oxidation device according to claim 1 further includes: An adjustment effluent area for adjusting the pH of the wastewater output from the residual oxidation species elimination area and outputting wastewater suitable for biochemical treatment; Wherein, the total hydraulic retention time of the primary oxidation area, the secondary oxidation area, the tertiary oxidation area and the residual oxidation species elimination area is 60 to 80 minutes.

8. A wastewater oxidation method using the wastewater oxidation device according to any one of claims 1 to 7, comprising the following steps: Adjust the pH of the wastewater to be treated; Through O3 / Fe 2+ / calcium peroxide / Oxone oxidation system to perform primary oxidation treatment on the pH-adjusted wastewater to obtain primary treated wastewater; Perform secondary oxidation treatment on the primary treated wastewater through an O3 / activated carbon / H2O2 / Oxone oxidation system to obtain secondary treated wastewater; Perform tertiary oxidation treatment on the secondary treated wastewater through an O3 / ultraviolet light / persulfate / Oxone oxidation system to obtain tertiary treated wastewater; After the tertiary oxidation treatment, the output wastewater is suitable for further biochemical treatment.

9. According to the wastewater oxidation method of claim 8, wherein: The O3 / Fe 2+ / calcium peroxide / Oxone oxidation system includes: 4 - 6 mg / L of O3, 19 - 21 mg / L of Fe 2+ , 24 - 26 mg / L of calcium peroxide and 16 - 18 mg / L of Oxone; The O3 / activated carbon / H2O2 / Oxone oxidation system includes: 5 to 7 mg / L of O3, 12 to 14 mg / L of activated carbon, 0.12 to 0.13 ml / L of 30 wt% H2O2 and 15 to 17 mg / L of Oxone; The O3 / ultraviolet light / persulfate / Oxone oxidation system includes: ultraviolet light of 240 to 260 nm and 5 to 8 W, 6 to 8 mg / L of O3, 16 to 18 mg / L of persulfate and 14 to 16 mg / L of Oxone.

10. According to the wastewater oxidation method of claim 8, further includes: After performing reduction treatment and pH adjustment on the tertiary treated wastewater, output wastewater suitable for biochemical treatment.

11. The wastewater oxidation method according to claim 10, wherein, The wastewater to be treated is the biochemical effluent of traditional Chinese medicine preparation wastewater, with a COD of 380 - 400 mg / L, a chromaticity of 95 - 115 times, a pH of 6 - 9, a BOD5 / COD of 0.08 - 0.11, and a biodegradation rate of 0.12 - 0.14 d -1 .

12. The wastewater oxidation method according to claim 10, wherein, The pH of the wastewater to be treated is adjusted to 5.7 to 6.3, and the pH of the tertiary treated wastewater is adjusted to 7.2 to 7.4.

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