Method for treating white spirit brewing wastewater by coupling ozone and activated carbon filter tank

Abstract

The invention belongs to the field of wastewater treatment, and particularly relates to a method for treating white spirit brewing wastewater by coupling ozone and an activated carbon filter tank, namely sequentially carrying out biochemical treatment, ozone oxidation, activated carbon treatment, coagulation treatment and precipitation on the white spirit brewing wastewater to finally obtain produced water meeting the emission limit value. The white spirit brewing wastewater treated by the method disclosed by the invention can be discharged at a discharge limit value superior to the discharge standard of water pollutants for fermented alcohol and white spirit industry (GB 27631-2011). According to the method disclosed by the invention, the treatment cost of catalytic ozonation can be effectively reduced, the removal rate of pollutants is improved, and the service life of activated carbon is prolonged.

Description

Technical Field

[0001] The invention belongs to the field of wastewater treatment, and in particular relates to a method for treating liquor brewing wastewater by coupling ozone with an activated carbon filter. Background Art

[0002] In the process of liquor wastewater treatment, because the wastewater contains some organic pollutants that are difficult to biodegrade, it is difficult for general biochemical system treatment technology to make the pollutants in the wastewater meet the emission standards after treatment.

[0003] At present, the common practice is to add solutions such as ozone oxidation and activated carbon filter to the liquor wastewater treatment system, using the strong oxidizing properties of ozone to oxidize the organic matter that is difficult to biodegrade in the wastewater, or using the adsorption properties of activated carbon to adsorb and remove the residual organic pollutants in the wastewater. However, in actual engineering applications, the removal rate of residual organic pollutants in water is generally around 50%, which is still difficult to meet the limit required by the emission standards; the method of using ozone oxidation often leads to poor oxidation effect due to low ozone utilization; the method of using activated carbon adsorption often causes the activated carbon adsorption to become saturated and ineffective, with a short service life and high operating costs. Therefore, it is very important to develop a wastewater treatment method that can make full use of ozone and long-term use of activated carbon. Summary of the invention

[0004] The present invention aims to provide a method for treating liquor brewing wastewater by coupling ozone with an activated carbon filter, which can effectively improve the efficiency of ozone oxidation, while increasing the service life of activated carbon, reducing operating costs, and improving the effluent water quality of treated wastewater.

[0005] The present invention provides a method for treating liquor brewing wastewater, comprising the following steps:

[0006] (1) obtaining liquor brewing wastewater;

[0007] (2) allowing the liquor brewing wastewater described in step (1) to enter an ozone reaction tank to obtain wastewater after ozone oxidation reaction;

[0008] (3) allowing the wastewater after the ozone oxidation reaction in step (2) to enter an activated carbon filter to obtain wastewater treated with activated carbon;

[0009] (4) allowing the wastewater treated with activated carbon in step (3) to enter a coagulation reaction tank to obtain wastewater treated with a coagulant;

[0010] (5) The wastewater treated with the coagulant in step (4) enters a sedimentation tank to obtain a supernatant after precipitation, and then enters a discharge port for discharge.

[0011] In some embodiments, the liquor brewing wastewater includes Maotai-flavor liquor brewing wastewater.

[0012] In some embodiments, in step (1), obtaining liquor brewing wastewater includes biochemically treating the liquor brewing wastewater, and then the biochemically treated wastewater enters the ozone reaction tank.

[0013] In some embodiments, the method is a method for treating liquor brewing wastewater by coupling ozone with an activated carbon filter.

[0014] In some implementation schemes, an activated carbon filter is set immediately after the ozone reaction tank, and an aeration device is set in the activated carbon filter, so that organic pollutants and ozone molecules in the water can be enriched on the surface of the activated carbon, forming a high concentration of organic pollutants and ozone environment, thereby improving the efficiency of ozone oxidation.

[0015] In some embodiments, activated carbon simultaneously adsorbs organic pollutants and ozone molecules, which can form a strong oxidizing environment on the surface of the activated carbon, oxidizing the organic pollutants adsorbed by the activated carbon into carbon dioxide and water, thereby achieving the recycling regeneration of the activated carbon and extending the service life of the activated carbon.

[0016] In some embodiments, the biochemical treatment includes anaerobic treatment, aerobic treatment or A / O process treatment.

[0017] In some embodiments, an aeration device is installed at the bottom of the ozone reaction tank in step (2), and the ozone-containing gas is distributed in the tank through the aeration device.

[0018] In some embodiments, the aeration device is one or more of an aeration plate, an aeration tube, and an aerator.

[0019] In some embodiments, the aeration device is an aeration disk.

[0020] In some embodiments, the aeration disk comprises a titanium alloy aeration disk.

[0021] In some embodiments, the aeration plates are evenly distributed.

[0022] In some embodiments, the ozone reaction tank in step (2) is filled with ball ring packing.

[0023] In some embodiments, the ball ring packing is a stainless steel ball ring packing.

[0024] In some embodiments, the packing height of the ball ring packing is 0.5-5 meters.

[0025] In some embodiments, the packing height of the ball ring packing is 0.5-3 meters.

[0026] In some embodiments, the packing height of the ball ring packing is 1-2 meters.

[0027] In some embodiments, the specific area to be filled is the area between 0.5 meters and 2.5 meters from the bottom of the ozone reaction tank.

[0028] In some embodiments, the specific area to be filled is the area between 0.5 meters and 2.0 meters from the bottom of the ozone reaction tank.

[0029] In some embodiments, the specific area to be filled is the area between 0.5 meters and 1.5 meters from the bottom of the ozone reaction tank.

[0030] In some embodiments, an aeration device is provided at the bottom of the ozone reaction tank and ball ring fillers are filled so that ozone can fully react with organic pollutants in the wastewater, thereby effectively improving the efficiency of ozone oxidation.

[0031] In some embodiments, the residence time of the liquor brewing wastewater in the ozone reaction tank is 10-120 min.

[0032] In some embodiments, the residence time of the liquor brewing wastewater in the ozone reaction tank is 15-80 minutes.

[0033] In some embodiments, the residence time of the liquor brewing wastewater in the ozone reaction tank is 30-50 minutes.

[0034] In some embodiments, the amount of ozone added to the ozone reaction tank is calculated based on the COD in the wastewater, and ozone is added at an O / C value of 0.5-8.0.

[0035] In some embodiments, ozone is added at the O / C value = 1.0-5.0.

[0036] In some embodiments, ozone is added at the O / C value = 1.0-4.0.

[0037] In some embodiments, the O / C value is the mass ratio of O3 to COD.

[0038] In some embodiments, the activated carbon filter in step (3) is selected from at least one of a gravity downflow activated carbon filter, a V-type activated carbon filter and a pressure activated carbon filter.

[0039] In some embodiments, the activated carbon filter is a gravity downflow activated carbon filter.

[0040] In some embodiments, an aeration device is provided at the bottom of the activated carbon filter.

[0041] In some embodiments, the aeration device is one or more of an aeration plate, an aeration tube, and an aerator.

[0042] In some embodiments, the aeration device is an aeration tube.

[0043] In some embodiments, the activated carbon filling height of the activated carbon filter is 0.5-10 meters.

[0044] In some embodiments, the activated carbon filling height of the activated carbon filter is 0.5-6 meters.

[0045] In some embodiments, the activated carbon filling height of the activated carbon filter is 1-4 meters.

[0046] In some embodiments, the activated carbon filling height of the activated carbon filter is 1-2 meters.

[0047] In some embodiments, the activated carbon filling area of ​​the activated carbon filter is an area from 1 meter to 10 meters from the bottom of the activated carbon filter.

[0048] In some embodiments, the activated carbon filling area of ​​the activated carbon filter is an area from 2 meters to 6 meters from the bottom of the activated carbon filter.

[0049] In some embodiments, the activated carbon filling area of ​​the activated carbon filter is an area from 2 meters to 4 meters from the bottom of the activated carbon filter.

[0050] In some embodiments, the bottom of the activated carbon filling area is also filled with pebbles and quartz sand.

[0051] In some embodiments, in step (3), the residence time of the wastewater after the ozone oxidation reaction in the activated carbon filter is 5-120 min.

[0052] In some embodiments, the residence time of the wastewater after the ozone oxidation reaction in the activated carbon filter is 10-90 minutes.

[0053] In some embodiments, the residence time of the wastewater after the ozone oxidation reaction in the activated carbon filter is 15-60 minutes.

[0054] In some embodiments, the coagulant includes polyaluminium chloride, polyacrylamide or polyferric sulfate.

[0055] In some embodiments, the concentration of the polyaluminium chloride is based on the volume of the wastewater entering the coagulation reaction tank, and the mass of the polyaluminium chloride contained in the coagulation reaction tank accounts for the proportion of the wastewater entering the coagulation reaction tank.

[0056] In some embodiments, the concentration of the polyaluminium chloride is 0.05-5.0 kg / m 3 .

[0057] In some embodiments, the concentration of the polyaluminium chloride is 0.05-4.0 kg / m 3 .

[0058] In some embodiments, the concentration of the polyaluminium chloride is 0.05-2.5 kg / m 3 .

[0059] In some embodiments, the concentration of the polyaluminium chloride is 0.05-1.0 kg / m 3 .

[0060] In some embodiments, the concentration of the polyaluminium chloride is 0.10-0.7 kg / m 3 .

[0061] In some embodiments, the concentration of the polyaluminium chloride is 0.15-0.3 kg / m 3 .

[0062] In some embodiments, the concentration of the polyaluminium chloride is 0.15-0.25 kg / m 3 .

[0063] In some embodiments, the coagulant includes polyaluminium chloride and polyacrylamide.

[0064] In some embodiments, the mass of polyaluminium chloride contained in the coagulation reaction tank is the mass of commercial polyaluminium chloride.

[0065] In some embodiments, the concentration of the polyacrylamide is based on the volume of the wastewater entering the coagulation reaction tank, and the mass of the polyacrylamide contained in the coagulation reaction tank accounts for the proportion of the wastewater entering the coagulation reaction tank.

[0066] In some embodiments, the concentration of the polyacrylamide is in the range of 0.001 kg / m 3 Up to 0.1kg / m 3 .

[0067] In some embodiments, the concentration of the polyacrylamide is in the range of 0.005 kg / m 3 Up to 0.05kg / m 3 .

[0068] In some embodiments, the mass of polyacrylamide contained in the coagulation reaction tank is the mass of commercial polyacrylamide.

[0069] In some embodiments, the treatment time of the coagulant is 5-60 minutes.

[0070] In some embodiments, the treatment time of the coagulant is 10-30 minutes.

[0071] The invention also provides an application of the method for treating liquor brewing wastewater in treating fermented alcohol or liquor industry wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Figure 1 The present invention is a process flow chart of a method for treating liquor brewing wastewater by coupling ozone and activated carbon filter. DETAILED DESCRIPTION

[0073] The technical solution of the present invention is further described below by specific embodiments, which do not limit the protection scope of the present invention. Some non-essential modifications and adjustments made by others based on the concept of the present invention still fall within the protection scope of the present invention.

[0074] In the examples of this article, the emission limits in the water quality test results are the direct emission limits of the relevant indicators given in Table 3 of the "Emission Standard of Water Pollutants for Fermentation Alcohol and Liquor Industry" (GB 27631-2011).

[0075] In the embodiment of this article, the pollutant removal rate of the ozone reaction tank = 1-(concentration of the relevant index of the ozone reaction tank water production / concentration of the relevant index of the ozone reaction tank water inlet)*100%.

[0076] In the examples herein, the pollutant removal rate of the activated carbon filter=1-(concentration of the relevant index of the water produced by the activated carbon filter / concentration of the relevant index of the water produced by the ozone reaction tank)*100%.

[0077] In the examples herein, the ozone-activated carbon coupling pollutant removal rate = 1 - (concentration of indicators related to water produced by the activated carbon filter / concentration of indicators related to water in the ozone reaction tank) * 100%.

[0078] In the examples of this article, the system removal rate = 1-(concentration of relevant indicators of water produced by the sedimentation tank / concentration of relevant indicators of water inlet of the ozone reaction tank)*100%.

[0079] In the examples herein, the iodine adsorption value reduction rate=1-(7-day or 14-day iodine adsorption value / 0-day iodine adsorption value)*100%.

[0080] In the embodiment of this article, the specific steps of biochemical treatment are first anaerobic treatment by anaerobic baffled reactor (ABR) and upflow anaerobic sludge blanket (UASB), and then aerobic treatment by five-stage bardenpho. The above operations are respectively carried out with reference to the method disclosed by Ma Longling et al. (Ma Longling, Tang Yankui, Zhang Hanbing. Design of baffled anaerobic reactor [J]. Journal of Guangxi University (Natural Science Edition), 2008, 33 (S1): 378-380. DOI: 10.13624 / j.cnki.issn.1001-7445.2008.s1.031.), "Technical Specifications for Upflow Anaerobic Sludge Blanket Reactor Wastewater Treatment Engineering (HJ 2013-2012)" and "Technical Specifications for Anaerobic-Anoxic-Aerobic Activated Sludge Process Wastewater Treatment Engineering (HJ 576-2010)".

[0081] "Biochemical treatment", the full name of which is biochemical treatment, refers to a wastewater treatment method that uses the life activities of microorganisms to effectively remove soluble organic matter and some insoluble organic matter in wastewater.

[0082] In the embodiments herein, the process flow of the method for treating liquor brewing wastewater by coupling ozone with an activated carbon filter is disclosed as follows: Figure 1 As shown, the arrow indicates the direction of water flow. The water produced by the biochemical treatment enters from the bottom of the ozone reaction tank, passes through the ball ring packing from bottom to top, and is oxidized by the ozone released by the aeration disk; the water produced by the ozone reaction tank enters from the upper part of the activated carbon filter tank, and after the water is discharged from the bottom, the wastewater enters the coagulation reaction tank; the coagulation reaction tank is equipped with a mixer, under the action of the mixer, the coagulant added can be fully mixed and reacted with the wastewater; the water produced by the coagulation reaction tank enters from the middle of the sedimentation tank, the sediment sinks to the bottom of the sedimentation tank, and the wastewater is discharged from the upper part of the sedimentation tank through the discharge port. Among them, titanium alloy aeration plates are evenly arranged at the bottom of the ozone reaction tank, and a stainless steel channel steel frame is installed 0.5m away from the bottom of the ozone reaction tank. A stainless steel wire mesh is laid on the steel frame, and 316 stainless steel ball ring fillers are filled on the wire mesh to a height of 1.5m from the bottom of the ozone reaction tank; the activated carbon filter is a gravity downflow activated carbon filter, and an aeration pipe is set at the bottom of the activated carbon filter. There is a filter plate at a position 1.5m to 2m away from the bottom of the activated carbon filter. Pebbles and quartz sand are laid on the filter plate from bottom to top. The laying area of ​​activated carbon is The area is 2m to 4m away from the bottom of the activated carbon filter tank; the coagulants used in the coagulation reaction are polyaluminum chloride and polyacrylamide. The mass of polyaluminum chloride products and polyacrylamide products to be added is calculated in advance based on the volume of wastewater that will enter the coagulation reaction tank and the concentration values ​​of polyaluminum chloride and polyacrylamide. After the wastewater enters the coagulation reaction tank, the corresponding mass of polyaluminum chloride products and polyacrylamide products are added, and the polyaluminum chloride and polyacrylamide are fully contacted and reacted with the wastewater through a mixer.

[0083] In the embodiments herein, the CODcr determination method refers to the "Determination of Chemical Oxygen Demand of Water Quality - Dichromate Method" (HJ828-2017), the ammonia nitrogen determination method refers to the "Determination of Ammonia Nitrogen in Water Quality - Nessler's Reagent Spectrophotometric Method" (HJ 535-2009), the total phosphorus determination method refers to the "Determination of Total Phosphorus in Water Quality - Ammonium Molybdate Spectrophotometric Method" (GB 11893-89), the colorimetric determination method refers to the "Water Quality Colorimetric Determination Dilution Multiple Method" (HJ 1182-2021), and the determination method of activated carbon iodine adsorption value refers to the "Test Method for Coal-Based Granular Activated Carbon - Determination of Iodine Adsorption Value" (GB / T 7702.7-2008).

[0084] In Comparative Example 2 of this article, the function of the intermediate water tank is to store wastewater. In Comparative Example 2, an intermediate water tank is added between the ozone reaction tank and the activated carbon filter tank in order to interrupt the coupling of the ozone-activated carbon filter tank, thereby judging the effect of the coupling of the ozone and the activated carbon filter tank on the adsorption performance of the activated carbon by the decrease in the iodine adsorption value of the activated carbon.

[0085] In the embodiments of this invention, the ball ring packing (size: 16*16*0.3mm, item number: 0004739) used is from Zhejiang Weijia Special Steel Co., Ltd.; the aeration plate (item number: 00007328) is from Jiangsu Xinqiguang Environmental Technology Co., Ltd.; the aeration tube is from Jiangsu Jinrun Environmental Engineering Co., Ltd.; solid polyaluminium chloride (Qingyuan brand, containing 30% alumina by mass) is from Shenzhen Changlong Technology Co., Ltd.; polyacrylamide (model: SA-150) is from Henan Wanxiang Water Treatment Materials Co., Ltd.

[0086] In this article, the professional terms in this field are explained as follows:

[0087] The coupling of ozone and activated carbon filter refers to the phenomenon that the ozone reaction tank and the activated carbon filter cooperate closely through direct connection and influence each other.

[0088] COD refers to chemical oxygen demand; CODcr refers to the chemical oxygen demand measured using potassium dichromate as an oxidant, also known as the dichromate index.

[0089] The O / C value refers to the mass ratio of O3 to COD.

[0090] A / O process treatment refers to the anoxic-aerobic activated sludge method.

[0091] The system removal rate refers to the removal effect of the method disclosed in the present invention for treating wastewater generated in the brewing process of Maotai-flavor liquor by coupling ozone and activated carbon filter tank for related pollutants. The calculation formula in the embodiment is 1-(concentration of related indicators of water production in the sedimentation tank / concentration of related indicators of water inlet in the ozone reaction tank)*100%.

[0092] High-concentration liquor brewing wastewater refers to liquor brewing wastewater with a higher concentration of organic matter due to differences in production cycles.

[0093] Daily processing capacity refers to the actual capacity of a sewage treatment plant (or treatment device) to process sewage every day and night.

[0094] The daily treatment design capacity refers to the design capacity of a sewage treatment plant (or treatment device) to treat sewage every day and night.

[0095] The wastewater design flow rate refers to the daily treatment design capacity of the sewage treatment plant (or treatment device) / 24h.

[0096] In the following examples, the concentration of polyaluminium chloride is 0.2 kg / m 3 , refers to the volume of wastewater entering the coagulation reaction tank, 1m 3 The wastewater contains 0.2 kg of polyaluminium chloride, where the 0.2 kg refers to the mass of the purchased polyaluminium chloride itself; the same is true for the concentration of polyacrylamide.

[0097] Example 1

[0098] The present invention provides a method for treating wastewater generated in the brewing process of Maotai-flavor liquor by coupling ozone with an activated carbon filter, which is used for treating water produced by a biochemical system of a liquor wastewater treatment plant. Specifically, the method comprises the following steps: (1) the Maotai-flavor liquor brewing wastewater is biochemically treated (the method refers to the literature "Design of Baffled Anaerobic Reactor", "Technical Specification for Wastewater Treatment Engineering of Upflow Anaerobic Sludge Bed Reactor (HJ 2013-2012)" and "Technical Specification for Wastewater Treatment Engineering of Anaerobic-Anoxic-Aerobic Activated Sludge Process (HJ 2013-2012)" by Ma Longling et al. 576-2010)》) to obtain wastewater after biochemical treatment; (2) the wastewater after biochemical treatment enters the ozone reaction tank for ozone oxidation reaction to obtain wastewater after ozone oxidation reaction; (3) the wastewater after ozone oxidation reaction enters the activated carbon filter tank to enrich ozone and organic pollutants in the water, and further catalytic oxidation is obtained on the surface of activated carbon to obtain wastewater treated with activated carbon; (4) the wastewater after activated carbon treatment enters the coagulation reaction tank to obtain wastewater treated with coagulant; (5) the wastewater after coagulant treatment enters the sedimentation tank for sedimentation treatment to obtain supernatant, which is water that meets the limit value required by the emission standards, and enters the discharge port.

[0099] This method includes the use of an ozone reaction tank, an activated carbon filter, a coagulation reaction tank, a sedimentation tank and its ancillary equipment. Figure 1As shown, the arrow indicates the direction of water flow. The biochemically treated Maotai-flavor liquor brewing wastewater enters the ozone reaction tank, where it stays for 40 minutes, and the amount of ozone is added according to the O / C value = 1.5; after the wastewater completes the reaction in the ozone reaction tank, it enters the activated carbon filter tank, where it stays for 30 minutes; after the wastewater completes the reaction in the activated carbon filter tank, it enters the coagulation reaction tank, where it reacts for 20 minutes; calculated based on the volume of wastewater entering the coagulation reaction tank, the concentration of polyaluminium chloride is 0.2kg / m 3 , polyacrylamide concentration is 0.03kg / m 3 After the coagulation reaction is completed, the supernatant is obtained through sedimentation in the sedimentation tank and enters the discharge port.

[0100] The water quality of the produced water after treatment in each link was tested, and the test results are shown in Table 1.

[0101] Table 1 Example 1 Water quality test results

[0102]

[0103]

[0104] As can be seen from Table 1, the method for treating wastewater generated in the brewing process of Maotai-flavor liquor by coupling ozone and activated carbon filter provided by the present invention can produce water that is significantly better than the discharge standard of industrial water pollutants for fermented alcohol and liquor, thereby ensuring the water quality of the water produced at the drain outlet.

[0105] Example 2

[0106] The present invention provides a method for treating wastewater generated in the brewing process of Maotai-flavor liquor by coupling ozone with an activated carbon filter tank, which is used for water treatment in a biochemical system of a liquor wastewater treatment plant. Specifically, the method comprises the following steps: (1) the Maotai-flavor liquor brewing wastewater is subjected to biochemical treatment (same as in Example 1) to obtain biochemically treated wastewater; (2) the biochemically treated wastewater enters an ozone reaction tank for ozone oxidation reaction to obtain ozone-oxidized wastewater; (3) the ozone-oxidized wastewater enters an activated carbon filter tank to enrich ozone and organic pollutants in the water, and further catalytically oxidizes on the surface of activated carbon to obtain activated carbon-treated wastewater; (4) the activated carbon-treated wastewater enters a coagulation reaction tank to obtain coagulant-treated wastewater; (5) the coagulant-treated wastewater enters a sedimentation tank for sedimentation treatment to obtain supernatant, i.e., water that meets the limit value required by the emission standard, and enters a discharge port.

[0107] This method includes the use of an ozone reaction tank, an activated carbon filter, a coagulation reaction tank, a sedimentation tank and its ancillary equipment. Figure 1As shown, the arrow indicates the direction of water flow. The biochemically treated Maotai-flavor liquor brewing wastewater enters the ozone reaction tank, where it stays for 40 minutes, and the amount of ozone is added according to the O / C value = 2.0; after the wastewater completes the reaction in the ozone reaction tank, it enters the activated carbon filter tank, where it stays for 30 minutes; after the wastewater completes the reaction in the activated carbon filter tank, it enters the coagulation reaction tank, where it reacts for 20 minutes. Calculated based on the volume of wastewater entering the coagulation reaction tank, the concentration of polyaluminium chloride is 0.25kg / m 3 , polyacrylamide concentration is 0.03kg / m 3 After the coagulation reaction is completed, the supernatant is obtained through sedimentation in the sedimentation tank and enters the discharge port.

[0108] The water quality of the produced water after treatment in each link was tested, and the test results are shown in Table 2.

[0109] Table 2 Example 2 Water quality test results

[0110]

[0111]

[0112] As can be seen from Table 2, the method for treating wastewater generated in the brewing process of Maotai-flavor liquor by coupling ozone with an activated carbon filter provided by the present invention can produce water that is significantly better than the discharge standards for industrial water pollutants of fermented alcohol and liquor, thereby ensuring the quality of water produced at the outlet.

[0113] After replacing the new activated carbon, the method described in Example 2 was continued for 14 days, and the day when the wastewater entered the ozone reaction tank and started the reaction was regarded as Day 1. The iodine adsorption value of the activated carbon filter was tested, and the results are shown in Table 3.

[0114] Table 3 Example 2 Activated carbon filter iodine adsorption value test results

[0115] Time (day) Iodine adsorption value (mg / g) Iodine adsorption value reduction rate 0 987 0 7 962 2.5％ 14 934 5.4％

[0116] Example 3

[0117] The water produced by the biochemical system of a liquor wastewater treatment plant was treated, and the Maotai-flavor liquor brewing wastewater after biochemical treatment entered the ozone reaction tank. The residence time of the wastewater in the ozone reaction tank was 30min, 50min, and 60min respectively, and the amount of ozone was added according to the O / C value = 1.5; the produced water entered the activated carbon filter. Other steps not mentioned are the same as in Example 1.

[0118] The water quality of the influent and produced water of the ozone reaction tank was tested when the wastewater had different residence times in the ozone reaction tank. The test results are shown in Table 4.

[0119] Table 4 Example 3 Water quality test results

[0120]

[0121]

[0122] Combining Example 1 and Example 3, the pollutant removal rates of the ozone reaction tank when the wastewater has different residence times in the ozone reaction tank are compared, as shown in Table 5 below.

[0123] Table 5 Comparison of pollutant removal rates in ozone reaction tanks when wastewater stays in the ozone reaction tank for different times

[0124] The residence time of wastewater in the ozone reaction tank 30min 40min 50min 60min CODcr 45.5％ 61.4％ 63.5％ 64.3％ Ammonia nitrogen 10.5％ 18.5％ 19.3％ 19％ Total Phosphorus 2.5％ 6.7％ 7.2％ 7.6％

[0125] It can be seen from Table 5 that when the residence time of wastewater in the ozone reaction tank is 30 minutes, the pollutant removal rate of the ozone reaction tank is low; when the residence time of wastewater in the ozone reaction tank is 40 minutes, the pollutant removal rate of the ozone reaction tank is high, but the pollutant removal rate of the ozone reaction tank still has room for improvement; when the residence time of wastewater in the ozone reaction tank is 50 minutes, the pollutant removal rate of the ozone reaction tank is higher, and the pollutant treatment effect is good; when the residence time of wastewater in the ozone reaction tank is 60 minutes, the pollutant removal rate of the ozone reaction tank is high, and the pollutant treatment effect is good.

[0126] However, when the residence time of wastewater in the ozone reaction tank is 50min and 60min respectively, it can be found that with the increase of time, the wastewater treatment effect does not change much, but leads to a decrease in daily treatment capacity.

[0127] Therefore, it can be concluded that when the residence time of wastewater in the ozone reaction tank is less than 30 minutes, the pollutant removal effect of the ozone reaction tank is poor. When the residence time of wastewater in the ozone reaction tank is greater than 50 minutes, the pollutant removal effect of the ozone reaction tank is difficult to be better.

[0128] Example 4

[0129] The water produced by the biochemical system of a liquor wastewater treatment plant was treated, including the use of an ozone reaction tank, an activated carbon filter tank and its ancillary equipment. The biochemically treated Maotai-flavor liquor brewing wastewater enters the ozone reaction tank, and the residence time of the wastewater in the ozone reaction tank is 40 minutes. The amount of ozone is added according to the O / C value = 1.5; after the reaction is completed in the ozone reaction tank, it enters the activated carbon filter tank, and the residence time of the wastewater in the activated carbon filter tank is 10 minutes, 15 minutes, 25 minutes, 60 minutes, and 65 minutes respectively. The other steps are the same as in Example 1.

[0130] The water quality of the produced water after treatment in each link was tested, and the test results are shown in Table 6.

[0131] Table 6 Example 4 Water Quality Test Results

[0132]

[0133] Combining Example 1 and Example 4, the pollutant removal rates of the activated carbon filter when the wastewater stays in the activated carbon filter for different times are compared, as shown in Table 7 below.

[0134] Table 7 Comparison of pollutant removal rates in activated carbon filters when wastewater stays in the activated carbon filter for different times

[0135] Wastewater residence time in activated carbon filter 10min 15min 25min 30min 60min 65min CODcr 11.6％ 19.9％ 23.1％ 26.7％ 31.1％ 31.7％ Ammonia nitrogen 5.1％ 7.1％ 8.4％ 9.3％ 11.6％ 11.2％ Total Phosphorus 5.1％ 7.9％ 6.9％ 7.2％ 7.1％ 6.7％

[0136] It can be seen from Table 7 that when the residence time of wastewater in the activated carbon filter is 10 minutes, the pollutant removal rate of the activated carbon filter is low; when the residence time of wastewater in the activated carbon filter is 15 minutes, the pollutant removal rate of the activated carbon filter is low, but basically meets the process design requirements; when the residence time of wastewater in the activated carbon filter is 25 minutes, the pollutant removal rate of the activated carbon filter is average; when the residence time of wastewater in the activated carbon filter is 30 minutes, the pollutant removal rate of the activated carbon filter is high, and the pollutant treatment effect is good; when the residence time of wastewater in the activated carbon filter is 60 minutes, the pollutant removal rate of the activated carbon filter is high, and the pollutant treatment effect is good; when the residence time of wastewater in the activated carbon filter is 65 minutes, the pollutant removal rate of the activated carbon filter is high, and the pollutant treatment effect is good.

[0137] However, when the residence time of wastewater in the activated carbon filter is 60min and 65min respectively, it can be found that with the increase of time, the wastewater treatment effect does not change much, but leads to a decrease in daily treatment capacity.

[0138] Therefore, it can be concluded that when the residence time of wastewater in the activated carbon filter is less than 15 minutes, the pollutant removal effect of the activated carbon filter is too poor. When the residence time of wastewater in the activated carbon filter is greater than 60 minutes, the pollutant removal effect of the activated carbon filter is difficult to be better.

[0139] Example 5

[0140] The water produced by the biochemical system of a liquor wastewater treatment plant was treated, including the use of an ozone reaction tank, an activated carbon filter tank, a coagulation reaction tank, a sedimentation tank and its ancillary equipment. The Maotai-flavor liquor brewing wastewater that has undergone biochemical treatment enters the ozone reaction tank, where the wastewater stays for 40 minutes, and the amount of ozone is added according to the O / C value of 1.0, 3.0, 4.0, and 5.0 respectively; after the reaction is completed in the ozone reaction tank, it enters the activated carbon filter tank, where the wastewater stays for 30 minutes; after the reaction is completed in the activated carbon filter tank, the wastewater enters the coagulation reaction tank, where the wastewater reacts for 20 minutes. Calculated based on the volume of wastewater entering the coagulation reaction tank, the concentration of polyaluminium chloride is 0.25kg / m 3 , polyacrylamide concentration is 0.03kg / m 3 After the coagulation reaction is completed, the supernatant is obtained by sedimentation in a sedimentation tank and enters a discharge port. Other steps not mentioned are the same as those in Example 2.

[0141] The water quality of the produced water after treatment in each link was tested, and the test results are shown in Table 8.

[0142] Table 8 Example 5 Water Quality Testing Results

[0143]

[0144] Combining Example 2 and Example 5, the ozone-activated carbon coupling pollutant removal rates at different O / C values ​​are compared, as shown in Table 9 below.

[0145] Table 9 Comparison of pollutant removal rates by ozone-activated carbon coupling at different O / C values

[0146] O / C value 1.0 2.0 3.0 4.0 5.0 CODcr 65.6％ 75.8％ 74.6％ 76.1％ 75.3％ Ammonia nitrogen 40.7％ 41.5％ 45.9％ 48.4％ 48％ Total Phosphorus 6.0％ 6.3％ 6.8％ 8.1％ 8.4％

[0147] It can be seen from Tables 8 and 9 that when the amount of ozone is added according to the O / C value = 1.0, the ozone-activated carbon coupling pollutant removal rate is low, but the final sedimentation tank water production can basically meet the emission requirements, that is, the amount of ozone should be added according to the O / C value ≥ 1.0; when the amount of ozone is added according to the O / C value = 2.0, the removal rates of the three ozone-activated carbon coupling pollutants are significantly increased, and the sedimentation tank water production meets the emission requirements; when the amount of ozone is added according to the O / C value = 3.0, the ozone-activated carbon coupling removal rates of ammonia nitrogen and total phosphorus are significantly increased, and the sedimentation tank water production meets the emission requirements; when the amount of ozone is added according to the O / C value = 4.0, the removal rates of the three ozone-activated carbon coupling pollutants are further increased.

[0148] However, the ozone-activated carbon coupling removal rate of each pollutant does not change much when the amount of ozone added is based on O / C value = 4.0 compared with that added at O / C = 5.0. That is, the amount of ozone can be added when the O / C value is ≤ 4, otherwise it will cause a waste of operating costs.

[0149] Example 6

[0150] During the discharge of high-concentration liquor brewing wastewater, the biochemical system water of a liquor wastewater treatment plant was treated. After biochemical treatment (the method refers to the literature "Design of Baffled Anaerobic Reactor", "Technical Specification for Wastewater Treatment Engineering of Upflow Anaerobic Sludge Bed Reactor (HJ 2013-2012)" and "Technical Specification for Wastewater Treatment Engineering of Anaerobic-Anoxic-Aerobic Activated Sludge Process (HJ 576-2010)") by Ma Longling et al.), the high-concentration Maotai-flavor liquor brewing wastewater enters the ozone reaction tank. The residence time of the wastewater in the ozone reaction tank is 40 minutes, and the amount of ozone is added according to the O / C value = 1.5; after the reaction is completed in the ozone reaction tank, it enters the activated carbon filter tank, and the residence time of the wastewater in the activated carbon filter tank is 30 minutes; after the reaction is completed in the activated carbon filter tank, the wastewater enters the coagulation reaction tank, and the wastewater reacts in the coagulation reaction tank for 20 minutes. Calculated by the volume of wastewater entering the coagulation reaction tank, the concentrations of polyaluminium chloride are 0.1kg / m 3 , 0.15kg / m 3 , 0.25kg / m 3 , 0.3kg / m 3 , polyacrylamide concentration is 0.03kg / m 3 After the coagulation reaction is completed, the supernatant is obtained by sedimentation in the sedimentation tank and enters the discharge port. The total phosphorus index of the sedimentation tank effluent is tested, and the test results are shown in Table 10.

[0151] Table 10 Total phosphorus test results of sedimentation tank effluent in Example 6

[0152]

[0153]

[0154] It can be seen from Table 10 that during the discharge of high-concentration liquor brewing wastewater, the concentration of polyaluminium chloride should be ensured to be no less than 0.15kg / m 3 When the concentration of polyaluminium chloride reaches 0.25kg / m 3 After that, it is difficult to achieve better total phosphorus removal effect.

[0155] Comparative Example 1

[0156] The water produced by the biochemical system of a liquor wastewater treatment plant was treated. The Maotai-flavor liquor brewing wastewater that had been biochemically treated did not undergo ozone oxidation and directly entered the activated carbon filter tank. The residence time of the wastewater in the activated carbon filter tank was 30 minutes. After the wastewater completed the reaction in the activated carbon filter tank, it entered the coagulation reaction tank. The other steps not mentioned were the same as those in Example 2.

[0157] After replacing the new activated carbon, the method described in Comparative Example 1 was continued to operate for 14 days, and the time when the wastewater entered the ozone reaction tank and began to react was regarded as Day 1. The iodine adsorption value of the activated carbon filter was tested, and the results are shown in Table 11.

[0158] Table 11 Comparative Example 1 Activated Carbon Filter Iodine Adsorption Value Test Results

[0159] Time (day) Iodine adsorption value (mg / g) Iodine adsorption value reduction rate 0 1064 0 7 837 21.3％ 14 587 44.8％

[0160] It can be seen from Table 11 that when the wastewater is directly connected to the activated carbon filter without undergoing ozone catalytic oxidation, the activated carbon iodine adsorption value increases with the extension of the use time. Compared with the activated carbon iodine adsorption value in Example 2, the iodine adsorption value reduction rate shows a sharp upward trend, which means that the adsorption performance of the activated carbon decreases sharply.

[0161] Comparative Example 2

[0162] The water produced by the biochemical system of a liquor wastewater treatment plant is treated, and the Maotai-flavor liquor brewing wastewater after biochemical treatment enters the ozone reaction tank, and the residence time of the wastewater in the ozone reaction tank is 40 minutes, and the amount of ozone is added according to the O / C value = 2.0; after the wastewater completes the reaction in the ozone reaction tank, it enters the intermediate water tank, and the residence time in the intermediate water tank is the time obtained by dividing the volume of the intermediate water tank by the design flow rate of the wastewater. After passing through the intermediate water tank, the wastewater enters the activated carbon filter tank, and the residence time in the activated carbon filter tank is 30 minutes; after the wastewater completes the reaction in the activated carbon filter tank, it enters the coagulation reaction tank. Other steps not mentioned are the same as those in Example 2.

[0163] After replacing the new activated carbon, the method described in Comparative Example 2 was continued for 14 days, and the time when the wastewater entered the ozone reaction tank and started the reaction was regarded as Day 1. The iodine adsorption value of the activated carbon filter was tested, and the results are shown in Table 12.

[0164] Table 12 Comparative Example 2 Activated Carbon Filter Iodine Adsorption Value Test Results

[0165] Time (day) Iodine adsorption value (mg / g) Iodine adsorption value reduction rate 0 995 0 7 922 7.3％ 14 864 13.2％

[0166] It can be seen from Table 12 that when the wastewater is catalytically oxidized by ozone and then enters the activated carbon filter after passing through the intermediate water tank, the iodine adsorption value of the activated carbon increases with the extension of the use time. Compared with the iodine adsorption value of the activated carbon in Example 2, the iodine adsorption value reduction rate increases significantly, which means that the performance of the activated carbon decreases.

[0167] Comprehensively comparing Example 2 with Comparative Examples 1 and 2, when ozone is coupled with an activated carbon filter, the iodine adsorption value of the activated carbon decreases more slowly, which can extend the service life of the activated carbon.

Claims

1. A method for treating liquor brewing wastewater, characterized in that: The following steps are involved: (1) obtaining liquor brewing wastewater; (2) allowing the liquor brewing wastewater described in step (1) to enter an ozone reaction tank to obtain wastewater after ozone oxidation reaction; (3) allowing the wastewater after the ozone oxidation reaction in step (2) to enter an activated carbon filter to obtain wastewater treated with activated carbon; (4) allowing the wastewater treated with activated carbon in step (3) to enter a coagulation reaction tank to obtain wastewater treated with a coagulant; (5) The wastewater treated with the coagulant in step (4) enters a sedimentation tank to obtain a supernatant after precipitation, and then enters a discharge port for discharge.

2. The method according to claim 1, characterized in that The liquor brewing wastewater includes Maotai-flavor liquor brewing wastewater; Preferably, in step (1), obtaining liquor brewing wastewater comprises biochemically treating the liquor brewing wastewater, and then the biochemically treated wastewater enters the ozone reaction tank; Preferably, the method is a method for treating liquor brewing wastewater by coupling ozone with an activated carbon filter; Preferably, the biochemical treatment includes anaerobic treatment, aerobic treatment or A / O process treatment.

3. The method according to claim 1, characterized in that The ozone reaction tank in step (2) is provided with an aeration device at the bottom thereof, and the ozone-containing gas is distributed in the tank through the aeration device; Preferably, the aeration device is one or more of an aeration plate, an aeration tube, and an aerator; Preferably, the aeration device is an aeration disk; Preferably, the aeration disc comprises a titanium alloy aeration disc; Preferably, the aeration plates are evenly distributed.

4. The method according to claim 1, characterized in that The ozone reaction tank in step (2) is filled with ball ring filler; Preferably, the ball ring packing is a stainless steel ball ring packing; Preferably, the packing height of the ball ring packing is 0.5-5 meters; Preferably, the packing height of the ball ring packing is 0.5-3 meters; Preferably, the packing height of the ball ring packing is 1-2 meters; Preferably, the specific area of ​​the filling is the area from 0.5 meters to 2.5 meters from the bottom of the ozone reaction tank; Preferably, the specific area of ​​the filling is the area from 0.5 meters to 2.0 meters from the bottom of the ozone reaction tank; Preferably, the specific area for filling is the area from 0.5 meters to 1.5 meters from the bottom of the ozone reaction tank.

5. The method according to claim 1, characterized in that The residence time of the liquor brewing wastewater in the ozone reaction tank is 10-120 min; Preferably, the residence time of the liquor brewing wastewater in the ozone reaction tank is 15-80 min; Preferably, the residence time of the liquor brewing wastewater in the ozone reaction tank is 30-50 minutes.

6. The method according to claim 1, characterized in that The amount of ozone added to the ozone reaction tank is calculated based on the COD in the wastewater, and ozone is added at an O / C value of 0.5-8.0; Preferably, ozone is added at said O / C value = 1.0-5.0; Preferably, ozone is added at said O / C value = 1.0-4.0; Preferably, the O / C value is the mass ratio of O3 to COD.

7. The method according to claim 1, characterized in that The activated carbon filter in step (3) is selected from at least one of a gravity downflow activated carbon filter, a V-type activated carbon filter and a pressure activated carbon filter; Preferably, the activated carbon filter is a gravity downflow activated carbon filter; Preferably, an aeration device is provided at the bottom of the activated carbon filter tank; Preferably, the aeration device is one or more of an aeration plate, an aeration tube, and an aerator; Preferably, the aeration device is an aeration tube; Preferably, the activated carbon filling height of the activated carbon filter is 0.5-10 meters; Preferably, the activated carbon filling height of the activated carbon filter is 0.5-6 meters; Preferably, the activated carbon filling height of the activated carbon filter is 1-4 meters; Preferably, the activated carbon filling height of the activated carbon filter is 1-2 meters; Preferably, the activated carbon filling area of ​​the activated carbon filter is an area from 1 meter to 10 meters from the bottom of the activated carbon filter; Preferably, the activated carbon filling area of ​​the activated carbon filter is an area from 2 meters to 6 meters from the bottom of the activated carbon filter; Preferably, the activated carbon filling area of ​​the activated carbon filter is an area from 2 meters to 4 meters from the bottom of the activated carbon filter; Preferably, the bottom of the activated carbon filling area is also filled with pebbles and quartz sand.

8. The method according to claim 1, characterized in that In the step (3), the residence time of the wastewater after the ozone oxidation reaction in the activated carbon filter is 5-120 min; Preferably, the residence time of the wastewater after the ozone oxidation reaction in the activated carbon filter is 10-90 min; Preferably, the residence time of the wastewater after the ozone oxidation reaction in the activated carbon filter is 15-60 minutes.

9. The method according to any one of claims 1 to 8, characterized in that: The coagulant includes polyaluminium chloride, polyacrylamide or polyferric sulfate; Preferably, the concentration of the polyaluminium chloride is the ratio of the mass of the polyaluminium chloride contained in the coagulation reaction tank to the wastewater entering the coagulation reaction tank, with the volume of the wastewater entering the coagulation reaction tank as a reference; The concentration of the polyaluminium chloride is 0.05-5.0 kg / m 3 ; Preferably, the concentration of the polyaluminium chloride is 0.05-4.0 kg / m 3 ; Preferably, the concentration of the polyaluminium chloride is 0.05-2.5 kg / m 3 ; Preferably, the concentration of the polyaluminium chloride is 0.05-1.0 kg / m 3 ; Preferably, the concentration of the polyaluminium chloride is 0.10-0.7 kg / m 3 ; Preferably, the concentration of the polyaluminium chloride is 0.15-0.3 kg / m 3 ; Preferably, the concentration of the polyaluminium chloride is 0.15-0.25 kg / m 3 ; The coagulant includes polyaluminium chloride and polyacrylamide; Preferably, the mass of the polyaluminium chloride contained in the coagulation reaction tank is the mass of commercial polyaluminium chloride; Preferably, the concentration of the polyacrylamide is the ratio of the mass of the polyacrylamide contained in the coagulation reaction tank to the wastewater entering the coagulation reaction tank, with the volume of the wastewater entering the coagulation reaction tank as a reference; The concentration range of the polyacrylamide is 0.001 kg / m 3 Up to 0.1kg / m 3 ; Preferably, the concentration range of the polyacrylamide is 0.005 kg / m 3 Up to 0.05kg / m 3 ; Preferably, the mass of the polyacrylamide contained in the coagulation reaction tank is the mass of commercial polyacrylamide; Preferably, the treatment time of the coagulant is 5-60 min; Preferably, the treatment time of the coagulant is 10-30 min.

10. Use of the method according to any one of claims 1 to 9 in treating wastewater from fermented alcohol or liquor industries.

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