A method for degrading retinol derivatives and hydroquinone in cosmetic waste water

Abstract

The application discloses a method for degrading retinol derivatives and hydroquinone in cosmetic and plastic surgery wastewater, and belongs to the technical field of water treatment. The application aims at treating cosmetic drugs in cosmetic and plastic surgery wastewater, taking the cosmetic and plastic surgery wastewater as a treatment object, removing toxic drugs existing in the wastewater by using aerobic granular sludge (AGS) technology while making the cosmetic and plastic surgery wastewater meet the discharge standard, and successfully removing cosmetic pollutants, such as retinol derivatives and hydroquinone, which are used in a large amount, have great toxicity and are difficult to degrade in the environment.

Description

Technical Field

[0001] The invention relates to a method for degrading retinol derivatives and hydroquinone in antiseptic cosmetic wastewater, belonging to the technical field of water treatment. Background Art

[0002] Embalming and cosmetic wastewater is a type of wastewater unique to funeral homes. This type of wastewater consists of five parts: preservative waste liquid, body thawing water, body cleaning water, whole container equipment rinsing water, and cosmetic wastewater. This type of wastewater contains three types of pollutants that require special attention: (1) Nitrogen and phosphorus pollutants. These pollutants are relatively common, but due to the relatively low concentration of organic matter in the influent, the denitrification and phosphorus removal processes based on traditional microbial methods often have poor operating results; (2) Water microbial pollution has the disadvantages of wide distribution and enhanced toxicity due to the interaction of pathogenic bacteria. Among them, the Proteobacteria and Bacillus classes are relatively more numerous, and there is even a phenomenon of the growth of a large number of pathogenic microbial groups; (3) Antiseptic and cosmetic wastewater contains persistent and difficult-to-degrade special pollutants such as cosmetics and preservatives. The main components include chemicals such as sodium fatty alcohol ether sulfate (AES), cocopropyl betaine, parachloromethyl phenol (PCMX), coconut oil diethanolamide, flavors, glycerin, etc. Although the concentration of this type of wastewater is low, it is difficult to effectively remove it through pretreatment processes and ordinary activated sludge processes. Due to their biological toxicity, environmental persistence and bioaccumulation, they have significant environmental and health risks and will have a toxic effect on subsequent treatment processes, and even paralyze the biochemical treatment process.

[0003] The use of retinol and its derivatives in the global cosmetics industry has been increasing year by year. Commonly used retinol raw materials in the cosmetics industry include retinol, retinal, retinyl acetate, retinyl propionate, retinyl retinoate, and retinyl palmitate. Retinoic acid is a relatively irritating drug and is a prescription drug, prohibiting its use in cosmetics. Retinol products are relatively irritating, and those with intolerances may experience side effects such as redness, swelling, and peeling. Some products on the market, catering to consumer demand for rapid whitening and anti-aging effects, contain excessive amounts of retinol and its derivatives. Furthermore, the use of retinol and its derivatives in cosmetics presents challenges such as instability and low utilization rates. Residues of cosmetic pollutants in wastewater can enter the human body through the food chain, posing a health risk. Furthermore, micropollutants in cosmetic wastewater can affect the physiological functions of aquatic animals and disrupt ecological balance when entering receiving water bodies.

[0004] With the growing demand for cosmetics, research on their ingredients is gaining increasing attention. Phenolic pollutants, as essential organic synthetic materials, are widely used in industrial manufacturing. They are difficult to biodegrade, and their large-scale release into natural waters not only severely damages agriculture and fisheries, but also poses serious risks to human health and, in severe cases, life-threatening consequences. The impacts of phenols on human, animal, and plant health are chronic and can last for decades or longer. Hydroquinone, a representative phenolic pollutant, is an important intermediate in pesticides, pharmaceuticals, and dyes. It is also a key ingredient in the manufacture of anthraquinones, azo dyes, and photosensitive materials. It is also commonly used in rubber and food preservation, enjoying a wide range of applications. Hydroquinone, a skin lightener found in cosmetic cosmetics, is a difficult-to-remove micropollutant. Hydroquinone can be used as a skin-whitening agent, but studies have shown that frequent use can cause side effects such as dermatitis. Due to its low cost, availability, and effectiveness, it is often illegally added to cosmetics. Studies have shown that while hydroquinone can lighten dark spots and inhibit melanin production, it also has serious side effects. Long-term use can cause exogenous vitiligo and ochronosis. Furthermore, hydroquinone has a growth-inhibiting effect on aquatic organisms and is toxic to humans. Oral intake of 1g can cause acute poisoning, and 5g can be fatal.

[0005] Currently, there is no research work on cosmetic surgery wastewater. For the nitrogen and phosphorus pollutants contained therein, activated sludge processes including AAO (anaerobic / anoxic / aerobic process), SBR (sequential batch activated sludge process) and MBR (membrane bioreactor process) can be used for treatment. However, it is difficult to achieve a good degradation effect for cosmetics and preservatives that are difficult to degrade using activated sludge. Therefore, advanced oxidation technology based on electro-Fenton is generally used to remove them. However, electro-Fenton technology has the disadvantages of high dosage of reagents and large sludge output, which will increase the difficulty of processing and operating costs of the process. Therefore, establishing a safe, controllable and secondary pollution-free method for the degradation of cosmetics pollutants in cosmetic surgery wastewater is the focus and difficulty currently faced by water treatment.

[0006] Aerobic granular sludge (AGS) has garnered widespread attention in recent years due to its excellent settling properties, high biomass, high pollutant removal capacity, small footprint, and low operating costs in engineering applications. AGS plays a vital role in the treatment of domestic sewage, high-concentration organic wastewater, and wastewater rich in toxic and hazardous substances. It can efficiently remove nitrogen and phosphorus pollutants from sewage, and organic matter, toxic substances, and heavy metals from industrial wastewater. In recent years, AGS has also demonstrated advantages in removing emerging pollutants. AGS can remove nitrogen and phosphorus pollutants from cosmetic wastewater. Furthermore, due to its external biological protection mechanism and the anaerobic environment it creates, AGS can protect against recalcitrant and specific pollutants in cosmetic wastewater, such as cosmetics and preservatives. This allows for excellent nitrogen and phosphorus removal, as well as the removal of specific pollutants such as retinol derivatives and phenols. Summary of the Invention

[0007] Technical issues:

[0008] The present invention aims to provide a method for treating cosmetic drugs in embalming and cosmetic surgery wastewater. Taking embalming and cosmetic surgery wastewater as the treatment object, aerobic granular sludge (AGS) technology is used to remove toxic drugs present in the wastewater while ensuring that the embalming and cosmetic surgery wastewater meets the discharge standards. The present invention takes cosmetic pollutants that are used in large quantities, are highly toxic, and are difficult to degrade in the environment as an example, such as retinol derivatives and hydroquinone.

[0009] Technical solution:

[0010] The present invention provides a method for preparing aerobic granular sludge capable of removing toxic and harmful drugs in antiseptic cosmetic wastewater, comprising the following steps:

[0011] (1) Add wastewater and inoculated sludge into the SBR reactor;

[0012] (2) Controlling the duration of each operation cycle to 240-250 min, wherein the water inlet time is 5-10 min, the aeration time is 205-215 min, the settling time is 5-20 min, the drainage time is 5-10 min, the aeration volume is 2-2.5 L / min, the drainage ratio is 50-60%, and the reactor temperature is 20-25° C. After culturing for 35-45 days, fully granulated AGS is obtained;

[0013] (3) Adjust the COD and NH4 of the influent + -N is used for acclimation, and the adjustment method is as follows:

[0014] During the 1st to 8th day of acclimatization, the influent COD is 1200±20mg / L and the influent NH4 + -N is 60±10mg / L;

[0015] After 9-12 days of acclimatization, the influent COD is 1000±15mg / L and the influent NH4 + -N is 50±10mg / L;

[0016] At 13 to 18 days of acclimatization, the influent COD is 800±15mg / L and the influent NH4 + -N is 40±10mg / L;

[0017] At 19-25 days of acclimatization, the influent COD is 600±10mg / L and the influent NH4 + -N is 30±6mg / L;

[0018] At 26-32 days of acclimatization, the influent COD is 400±10mg / L and the influent NH4 + -N is 30±6mg / L;

[0019] At 33-40 days of acclimatization, the influent COD is 250±5mg / L and the influent NH4 + -N is 30±6mg / L;

[0020] Without changing other operating conditions, the AGS was acclimated for 40 to 50 days to obtain acclimated AGS;

[0021] (4) The influent is replaced with anti-corrosion cosmetic wastewater, and other operating conditions are not changed. The culture is carried out for 5 to 9 days, and finally aerobic granular sludge capable of removing preservatives in the wastewater is obtained.

[0022] Furthermore, in step (1), the height-to-diameter ratio of the SBR reactor is 8 to 12:1.

[0023] Specifically, in step (1), the height-to-diameter ratio of the SBR reactor is 10:1.

[0024] Furthermore, in step (1), the wastewater includes sodium acetate, sodium propionate, NH4Cl, K2HPO4, KH2PO4, MgSO4, CaCl2, ETDA and trace element concentrate; wherein, NaAc is 74.5-357 mg·L -1 Sodium propionate: 186.25~894mg·L -1 ; NH4Cl is 114.6~229mg·L -1 ; K2HPO4 is 40~44.8mg·L -1 ; KH2PO4 is 35~35.84mg·L -1 MgSO4 is 80-97 mg·L -1 ; CaCl2 is 70-75 mg·L -1 EDTA: 7-10 mg·L-1 .

[0025] Specifically, in step (1), the NaAc in the wastewater is 357 mg·L -1 ; Sodium propionate is 894 mg·L -1 ; NH4Cl is 229 mg·L -1 ; K2HPO4 is 44.8 mg·L -1 ; KH2PO4 is 35.84 mg·L -1 MgSO4 is 97 mg·L -1 ; CaCl2 is 75 mg·L -1 EDTA: 10 mg·L -1 .

[0026] Furthermore, the trace element concentrate includes ferric chloride, boric acid, copper sulfate, potassium iodide, manganese chloride, zinc chloride, cobalt chloride and sodium molybdate. In artificial simulated synthetic wastewater, the concentration of ferric chloride is 1-1.5 μg·L -1 The concentration of boric acid is 0.12-0.15 μg·L -1 The concentration of copper sulfate is 0.02-0.03 μg·L -1 The concentration of potassium iodide is 0.02-0.03 μg·L -1 The concentration of manganese chloride is 0.10~0.12μg·L -1 The concentration of zinc chloride is 0.04~0.058μg·L -1 The concentration of cobalt chloride is 0.10~0.15μg·L -1 , the concentration of sodium molybdate is 0.04~0.06μg·L -1 .

[0027] Specifically, the concentration of FeCl3·6H2O in the trace element concentrate is 1.35 μg·L -1 ; The concentration of H3BO3 is 0.135μg·L -1 The concentration of CuSO4·5H2O is 0.027 μg·L -1 ; The concentration of KI was 0.027 μg·L -1 ; The concentration of MnCl2·4H2O is 0.108μg·L -1 ; The concentration of ZnCl2 is 0.0522μg·L -1 ; The concentration of CoCl2·6H2O is 0.135μg·L -1 ;

[0028] The concentration of Na2MoO4·2H2O is 0.054 μg·L -1 .

[0029] Further, in step (1), the volume ratio of the trace element concentrate in the wastewater is 1:800-1000.

[0030] Specifically, in step (1), the volume ratio of the trace element concentrate in the wastewater is 1:800.

[0031] Further, in step (1), the COD of the wastewater is 1100-1300 mg / L, the NH4 + -N is 50-70 mg / L.

[0032] Specifically, in step (1), the COD of the wastewater is 1200±20 mg / L, the NH4 + -N is 60±10 mg / L.

[0033] Further, in step (1), the mixed liquid suspended solid concentration (MLSS) of the inoculated sludge is 4-6 g / L.

[0034] Specifically, in step (1), the mixed liquid suspended solid concentration (MLSS) of the inoculated sludge is 5 g / L.

[0035] Further, in step (1), the volume ratio of the wastewater to the inoculated sludge is 0.9:1-3.

[0036] Specifically, in step (1), the volume ratio of the wastewater to the inoculated sludge is 0.9:2.

[0037] Further, in step (1), the sludge age of the inoculated sludge is 20-30 d.

[0038] Specifically, in step (1), the sludge age of the inoculated sludge is 25 d.

[0039] Further, in step (2), the water in the influent in the cycle is the wastewater described in step (1).

[0040] Specifically, in step (2), the length of each running cycle is 240 min, the influent time is 5 min, the aeration time is 205 min, the aeration amount is 2.0 L / min, the sedimentation time is 5 min, the drainage time is 5 min, the drainage ratio is 50%, the reactor temperature is 25°C, and the cultivation is 40 d.

[0041] Further, the completely granulated sludge has a particle size of 0.43-0.88 mm.

[0042] Further, in step (3), the acclimation time is 40 days.

[0043] Further, in step (4), the corrosion and appearance correction wastewater, wherein the NaAc is 50-74.5 mg·L -1NaAc is 74.5mg·L -1 NH4Cl is 90~114.6mg·L -1 K2HPO4 is 5~7mg·L -1 KNO3 is 50~75mg·L -1 NaHCO3 is 140~155mg·L -1 MgSO4 is 20~50mg·L -1 CaCl2 is 20~35mg·L -1 EDTA is 5~10mg·L -1 .

[0044] Specifically, in step (4), the cosmetic and antiseptic wastewater is prevented, wherein NaAc is 74.5mg·L -1 NaAc is 186.25mg·L -1 NH4Cl is 114.6mg·L -1 K2HPO4 is 7mg·L -1 KNO3 is 75mg·L -1 NaHCO3 is 155mg·L -1 MgSO4 is 50mg·L -1 CaCl2 is 35mg·L -1 EDTA is 10mg·L -1 .

[0045] The application provides the aerobic granular sludge prepared according to the above steps.

[0046] The application provides the aerobic granular sludge prepared according to the above steps.

[0047] Further, the use includes denitrification and phosphorus removal, COD removal, heavy metal adsorption, retinol derivative and hydroquinone degradation.

[0048] The application provides a method for degrading retinol derivative and hydroquinone in cosmetic and antiseptic wastewater, comprising the following steps:

[0049] (1) adding cosmetic and antiseptic wastewater and the sludge particles prepared in the above steps into an SBR reactor;

[0050] (2) controlling the length of each operation cycle to be 240~250min, wherein the water inlet time is 5~10min, the aeration time is 205~215min, the sedimentation time is 5~20min, the water discharge time is 5~10min, the aeration amount is 2~2.5L / min, the water discharge ratio is 50~60%, and the reactor temperature is 20~25℃;

[0051] (3) After 5 to 7 days of treatment, the degradation of retinol derivatives and hydroquinone is completed.

[0052] Furthermore, the volume ratio of the sludge particles to the anti-corrosion and cosmetic wastewater is 1:3-10.

[0053] Preferably, the volume ratio of the sludge particles to the anti-corrosion and cosmetic wastewater is 1:5.

[0054] Furthermore, the antiseptic cosmetic wastewater is wastewater including retinol and its derivatives and / or hydroquinone.

[0055] Preferably, the antiseptic cosmetic wastewater is wastewater containing 7-15 mg / L of retinol and its derivatives and / or 3-7 mg / L of hydroquinone.

[0056] Specifically, the antiseptic cosmetic wastewater is wastewater containing 10 mg / L of retinol and its derivatives and / or 5 mg / L of hydroquinone.

[0057] Beneficial effects:

[0058] (1) The present invention introduces the anti-corrosion and cosmetic surgery wastewater into an aerobic granular sludge reactor, and aeration treatment can obtain wastewater that meets the emission standards. The anti-corrosion and cosmetic surgery wastewater is treated with AGS, which has a simple process and convenient operation and management. At the same time, only the AGS process can achieve good denitrification and phosphorus removal effects, and the special structure of AGS has a good stress resistance effect on toxic drugs in the anti-corrosion and cosmetic surgery wastewater.

[0059] (2) The cultured AGS of the present invention can be used to treat anti-corrosion cosmetic wastewater with a low influent concentration, and its removal rates for COD, total nitrogen and total phosphorus are as high as 86.88%, 78.24% and 84.55%, respectively.

[0060] (3) Aerobic granular sludge cultivated using the method of the present invention can achieve high removal rates for COD, total nitrogen, and total phosphorus in cosmetic wastewater containing retinol derivatives. The COD removal rate can reach as high as 84.17%, the TN removal rate can reach over 69.34%, and the TP removal rate is 85.12%. Furthermore, the removal rate of retinol palmitate in the wastewater, which can be removed through adsorption and degradation, is 85.20%.

[0061] (4) Aerobic granular sludge cultivated using the method of the present invention can achieve high removal rates for COD, total nitrogen, and total phosphorus in cosmetic wastewater containing hydroquinone. The COD removal rate can reach as high as 84.08%, the TN removal rate can reach over 69.28%, and the TP removal rate is 69.28%. Furthermore, the removal rate of hydroquinone in wastewater can be as high as 90.4% through adsorption and degradation. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 Schematic diagram of the aerobic granular sludge cultivation device.

[0063] Figure 2 This is a diagram showing the removal effect of COD, TN and TP in anti-corrosion and cosmetic wastewater by the domesticated AGS.

[0064] Figure 3 The removal effect of acclimated AGS on COD, TN, TP and retinyl palmitate in antiseptic cosmetic wastewater containing retinyl palmitate.

[0065] Figure 4 The removal effect of COD, TN, TP and hydroquinone in the anti-corrosion and cosmetic wastewater containing hydroquinone by the acclimated AGS. DETAILED DESCRIPTION

[0066] Source of raw materials:

[0067] Retinyl palmitate (brand: Aladdin, product number: MFCD00019414, purity: 96%) and hydroquinone (brand: McLean, product number: MFCD00002339, purity: 99%) were purchased from Huayuan.com. Unless otherwise specified, other raw materials used in the present invention were commercially available.

[0068] Example 1: Preparation of AGS

[0069] (1) Cultivation of AGS: The inoculated sludge was taken from a sewage treatment plant A. 2 The activated sludge in the aerobic tank of the / O process has an inoculation volume of 2 L and an MLSS concentration of 5.0 g / L. The test water inlet adopts artificial water distribution. The artificially prepared wastewater is transported into the reactor through a peristaltic pump with an inlet volume of 900 ml. The carbon source used for the artificially prepared wastewater is a mixed carbon source, in which NaAc is 357 mg·L -1 ; Sodium propionate is 894 mg·L -1 ; NH4Cl is 229 mg·L -1 ; K2HPO4 is 44.8 mg·L -1 ; KH2PO4 is 35.84 mg·L -1 MgSO4 is 97 mg·L -1 ; CaCl2 is 75 mg·L -1 EDTA: 10 mg·L -1 ; Trace elements 1ml. Trace element concentrate was prepared, and the trace element concentration in the inlet water was 1.5μg·L FeCl3·6H2O. -1 ; H3BO3 is 0.15μg·L -1 ; CuSO4·5H2O is 0.03μg·L -1 KI is 0.03 μg·L-1 ; MnCl2·4H2O is 0.12μg·L -1 ; ZnCl2 is 0.058μg·L -1 ; CoCl2·6H2O is 0.15μg·L -1 ; Na2MoO4·2H2O is 0.06μg·L -1 The COD of wastewater is 1200±20mg / L, NH4 + -N is 60±10mg / L.

[0070] The test device uses SBR with H / D of 10:1 ( Figure 1 ), an aeration device is set at the bottom of the reactor, and a rotor flowmeter is used to control the aeration volume of 2.0L / min in the oxygen flushing stage, so that AGS is formed as quickly as possible under high shear force and high hydraulic selection pressure. A time-controlled switch is used to control the status of each stage of the reactor. Each operation cycle includes four processes: water inlet, aeration, sedimentation, and drainage. The duration of each operation cycle is 240 minutes, of which the water inlet time is 5 minutes, the aeration time is 205 minutes, the sedimentation time is 5 minutes, the drainage time is 5 minutes, and the rest of the time is idle. The sedimentation time gradually shortens from 20 minutes to 5 minutes as the sludge granulation proceeds, and the drainage ratio is 50%. The sludge age is 25 days, and the reactor temperature is 25°C. After 40 days of cultivation in the reactor, fully granulated AGS is obtained, and the sludge particle size is between 0.43 mm and 0.88 mm.

[0071] (2) Acclimation of AGS

[0072] After the granulated AGS was successfully cultivated, in order to adapt the AGS to the anti-corrosion cosmetic wastewater, the COD was gradually reduced for acclimatization. The influent indicators are shown in Table 1. The original COD and NH4 + -N remains unchanged, then COD and NH4 + -N was gradually reduced for a total of 40 days of acclimation without changing other operating conditions, so that the microorganisms in the reactor could adapt to the low-concentration organic environment and obtain acclimated aerobic granular sludge.

[0073] Table 1 AGS culture water inlet index

[0074]

[0075]

[0076] (3) Adaptation of AGS

[0077] After the AGS was successfully domesticated, other operating conditions were not changed and the domesticated AGS was used to treat the anti-corrosion and cosmetic wastewater. The laboratory artificially prepared anti-corrosion and cosmetic wastewater, in which NaAc was 74.5 mg·L-1 ; Na2HPO4 7 mg / L -1 ; NH4Cl 114.6 mg / L -1 ; K2HPO4 7 mg / L -1 ; KNO3 75 mg / L -1 ; NaHCO3 155 mg / L -1 ; MgSO4 50 mg / L -1 ; CaCl2 35 mg / L -1 ; EDTA 10 mg / L -1 ; The water indicators measured after one week of culture all meet the first level A standard of Table 2 "Discharge Standard of Pollutants in Municipal Wastewater Treatment Plant" (GB 18918-2002). The pollutant removal effect within one week of reactor operation is shown in Figure 2 The figure shows that AGS has an adaptation period to the change of water quality, and the pollutant removal effect of AGS has a significant increase after one week of culture. The removal rates of COD, TN and TP increase from 70.39%, 66.84% and 61.95% on the 0th day to 86.88%, 78.24% and 84.55%, respectively.

[0078] Table 2 First level A standard of "Discharge Standard of Pollutants in Municipal Wastewater Treatment Plant"

[0079]

[0080] Table 3 Removal effect of each indicator after one week of operation

[0081]

[0082] Example 2: Removal of retinol derivatives by AGS

[0083] Retinol palmitate, a commonly used retinol derivative, was used as an example for removal experiments. SBR was used, and the AGS acclimated in step (3) of Example 1 was used as the inoculated sludge. The cosmetic and preservative wastewater containing retinol palmitate was treated, and the volume ratio of AGS to the cosmetic and preservative wastewater containing retinol palmitate was 1:5. The reaction period was consistent with the SBR in step (1) of Example 1. The influent was the artificial cosmetic and preservative wastewater prepared in step (3) of Example 1, wherein the concentration of retinol palmitate was 10 mg / L, and the other components were unchanged. Aeration was started (aeration amount was 2.0 L / min) and timing was started, and sampling was performed for one week for determination. The removal effects of pollutants and retinol palmitate are shown in Figure 3 and Table 4.

[0084] The results showed that the presence of retinyl palmitate had a certain effect on the acclimated AGS. After one day, the removal rates of COD, TN, TP, and retinyl palmitate by AGS were 32.80%, 35.56%, 50.00%, and 25.80%, respectively. The removal efficiency of AGS for retinyl palmitate improved significantly with the increase of reaction cycle. After seven days, the removal rates of COD, TN, TP, and retinyl palmitate were 84.17%, 69.34%, 85.12%, and 85.20%, respectively. This indicates that AGS can resist the toxicity of retinyl palmitate and may remove COD, total nitrogen, total phosphorus, and retinyl palmitate from wastewater through adsorption and degradation.

[0085] Table 4 AGS removal effect on retinol palmitate

[0086]

[0087] Example 3: Removal of hydroquinone from cosmetic surgery wastewater using AGS

[0088] SBR was used, and the AGS domesticated in step (3) of Example 1 was used as the inoculated sludge to treat the anti-corrosion and cosmetic wastewater added with hydroquinone. The volume ratio of AGS to the anti-corrosion and cosmetic wastewater with hydroquinone was 1:5, and the reaction cycle was the same as that of the SBR in step (1) of Example 1. The influent used the artificially prepared anti-corrosion and cosmetic wastewater in step (3) of Example 1, in which the concentration of hydroquinone added was 5 mg / L, and the other components remained unchanged. Aeration was started (the aeration volume was 2.0 L / min) and timing was started, and sampling was carried out for one week for measurement. The removal effect of pollutants and hydroquinone is shown in the figure. Figure 4 and as shown in Table 5.

[0089] The results showed that the presence of hydroquinone had a certain effect on the acclimated AGS. After one day, the removal rates of COD, TN, TP, and hydroquinone by AGS were 49.58%, 42.04%, 46.78%, and 33.4%, respectively. The removal efficiency of AGS for hydroquinone improved significantly with the increase of reaction period. After seven days, the removal rates of COD, TN, TP, and hydroquinone were 84.08%, 69.28%, 81.97%, and 90.4%, respectively. This indicates that AGS gradually adapted to the influent environment, was able to resist the toxicity of hydroquinone, and could remove COD, total nitrogen, total phosphorus, and hydroquinone from the wastewater through adsorption and degradation.

[0090] Table 5 AGS removal effect on hydroquinone

[0091]

[0092]

[0093] Comparative Example 1: Comparison of treatment effects of AGS and flocculent activated sludge

[0094] Preparation of flocculent activated sludge: Flocculent activated sludge was taken from the biochemical pool of a sewage treatment plant in Wuxi, and its MLSS was about 2.0 g / L.

[0095] 100 mL of settled AGS and flocculent activated sludge were added to the reactor respectively, the MLSS in the conical flask was controlled to be the same, and then the anti-corrosion cosmetic wastewater was added to 500 mL. The reaction cycle was consistent with the SBR in step (1) of Example 1. An aeration device was used to aerate it (the aeration volume was 2.0 L / min). Two parallel groups were set up for each sludge. Retinol palmitate (5 mg / L) and hydroquinone (10 mg / L) were added. The reaction cycle was consistent with the SBR. In order to better mix the mud and water in each conical flask, magnetic stirring was used for stirring at a speed of 200 rpm. The effluent was subjected to water quality and drug determination for 5 consecutive days, and the average removal rate of pollutants in the anti-corrosion cosmetic wastewater by the two sludges was calculated.

[0096] Table 6 Comparison of pollutant removal effects

[0097]

[0098] Although the present invention has been disclosed above in terms of preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A method for preparing aerobic granular sludge capable of removing retinol derivatives and hydroquinone from wastewater, characterized in that: The steps include: (1) Wastewater and inoculated sludge were added to the SBR reactor; the wastewater COD was 1100~1300 mg / L, NH4 + -N is 50~70mg / L; the inoculated sludge is taken from sewage treatment plant A 2 / O process aerobic tank activated sludge; the concentration of suspended solids in the mixed liquor of the inoculum sludge is 4~6 g / L; the volume ratio of wastewater to inoculum sludge is 0.9:1~3; (2) The duration of each operation cycle was controlled to be 240-250 min, wherein the water inlet time was 5-10 min, the aeration time was 205-215 min, the settling time was 5-20 min, the drainage time was 5-10 min, the aeration volume was 2-2.5 L / min, the drainage ratio was 50-60%, and the reactor temperature was 20-25 °C. After culturing for 35-45 days, fully granulated AGS was obtained. (3) Adjust the COD and NH4 of the influent + -N is used for acclimation, and the adjustment method is as follows: During the 1st to 8th day of acclimatization, the influent COD was 1200±20 mg / L and the influent NH4 + -N is 60±10 mg / L; On the 9th to 12th day of acclimatization, the influent COD was 1000±15 mg / L and the influent NH4 + -N is 50±10 mg / L; At 13-18 days of acclimatization, the influent COD was 800±15 mg / L and the influent NH4 + -N is 40±10 mg / L; During the 19th to 25th day of acclimatization, the influent COD was 600±10 mg / L and the influent NH4 + -N is 30±6 mg / L; At 26-32 days of acclimatization, the influent COD was 400±10 mg / L and the influent NH4 + -N is 30±6 mg / L; At 33-40 days of acclimatization, the influent COD was 250±5 mg / L and the influent NH4 + -N is 30±6 mg / L; Without changing other operating conditions, the AGS was acclimated for 40 to 50 days to obtain acclimated AGS; (4) The influent was replaced with anti-corrosion cosmetic wastewater, and other operating conditions were not changed. The culture was carried out for 5 to 9 days to finally obtain aerobic granular sludge capable of removing preservatives from the wastewater; the anti-corrosion cosmetic wastewater had a NaAc content of 50 to 74.5 mg·L -1 ; Sodium propionate: 150~186.25 mg·L -1 NH4Cl is 90~114.6 mg·L -1 ; K2HPO4 is 5~7 mg·L -1 ; KNO3 is 50~75 mg·L -1 ; NaHCO3 is 140~155 mg·L -1 MgSO4 is 20~50 mg·L -1 ; CaCl2 is 20~35 mg·L -1 EDTA: 5~10mg·L -1 .

2. The method according to claim 1, wherein In step (1), the height-to-diameter ratio of the SBR reactor is 8-12:

1.

3. The method according to claim 1, wherein In step (1), the wastewater includes sodium acetate, sodium propionate, NH4Cl, K2HPO4, KH2PO4, MgSO4, CaCl2, ETDA and trace element concentrate; wherein, NaAc is 74.5~357mg·L -1 Sodium propionate: 186.25~894mg·L -1 NH4Cl is 114.6~229 mg·L -1 ; K2HPO4 is 40~44.8mg·L -1 ; KH2PO4 is 35~35.84mg·L -1 MgSO4 is 80~97 mg·L -1 ; CaCl2 is 70~75 mg·L -1 EDTA: 7~10 mg·L -1 ; The concentration of ferric chloride is 1~1.5µg·L -1 The concentration of boric acid is 0.12~0.15 μg·L -1 The concentration of copper sulfate is 0.02~0.03 μg·L -1 The concentration of potassium iodide is 0.02~0.03 μg·L -1 , the concentration of manganese chloride is 0.10~0.12 μg·L -1 The concentration of zinc chloride is 0.04~0.058 μg·L -1 The concentration of cobalt chloride is 0.10~0.15 μg·L -1 The concentration of sodium molybdate is 0.04~0.06 μg·L -1 .

4. Aerobic granular sludge prepared according to the method according to any one of claims 1 to 3.

5. Use of the aerobic granular sludge according to claim 4 in wastewater treatment.

6. A method for degrading retinol derivatives and hydroquinone in cosmetic surgery wastewater, characterized in that: The steps include: (1) Adding the anti-corrosion cosmetic wastewater and the sludge particles described in claim 4 to the SBR reactor; (2) The duration of each operation cycle is controlled to be 240-250 min, including water inlet time of 5-10 min, aeration time of 205-215 min, sedimentation time of 5-20 min, drainage time of 5-10 min, aeration volume of 2-2.5 L / min, drainage ratio of 50-60%, and reactor temperature of 20-25 °C; (3) After 5 to 7 days of treatment, the degradation of retinol derivatives and hydroquinone is completed.

7. The method according to claim 6, characterized in that The volume ratio of sludge particles to anti-corrosion and cosmetic wastewater is 1:3~10.

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