Device and method for treating 1, 4-dioxane in waste spinning sewage

Abstract

The invention belongs to the technical field of chemical engineering and environmental protection, and discloses a device and a method for treating 1, 4-dioxane in waste spinning wastewater, the device comprises a homogenizing tank, an anaerobic expanded granular bed reactor, an aerobic biochemical reactor, an adsorption-biochemical co-synergistic reactor and a water outlet tank which are connected in sequence; wherein the adsorption-biochemical co-synergistic reactor is filled with a 1, 4-dioxane degradation filler; the 1, 4-dioxane degradation filler is prepared from the following raw materials: a 1, 4-dioxane degradation composite biological bacterial agent and a silane modified biozeolite carrier; the 1, 4-dioxane degradation composite biological bacterial agent comprises a 1, 4-dioxane composite biological bacterial agent, a biological accelerant and a biodegradable adhesive, the mass ratio of the 1, 4-dioxane composite biological agent to the biological accelerant to the biodegradable adhesive is 100: (5-10): (1-5); a granular sludge nucleating agent is added into the anaerobic expanded granular bed reactor. The method aims at the waste spinning wastewater, and organic pollutants in the wastewater can be effectively removed.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical industry and environmental protection, and more specifically, to a device and method for treating 1,4-dioxane in waste textile sewage. Background Art

[0002] The resource recovery of waste polyester textiles can effectively realize the recycling of waste polyester, which is an environmentally friendly and renewable process. The tail gas generated by each process unit in the regeneration and depolymerization process of waste polyester textiles needs to be treated by a tail gas washing tower before it can be discharged in compliance with the emission standards. The wastewater from the tail gas washing tower contains high concentrations of organic matter with complex components. Due to the formation of by-products in the production process, the wastewater also contains high concentrations of 1,4-dioxane. 1,4-Dioxane, an organic compound, is also known as dioxane and 1,4-dioxane. It is a colorless liquid with a slight fragrance. It is slightly toxic and irritating to the skin, eyes and respiratory system, and may cause damage to the liver, kidneys and nervous system. Acute poisoning may lead to death.

[0003] CN 106865733 A discloses a method for removing 1,4-dioxane from water, wherein 1,4-dioxane is removed from water by persulfate oxidation. However, the invention uses persulfate as an oxidant, and the reaction process requires heating, resulting in large amounts of reagent consumption and high costs.

[0004] CN 104710019 B discloses a method for treating chlorinated hydrocarbons / dioxanes by coupling zero-valent iron and activated sludge, wherein dioxanes are removed under anaerobic conditions by adding zero-valent iron to the activated sludge. However, the invention requires a large amount of zero-valent iron to be added, and the cost of treating the resulting excess activated sludge is high.

[0005] Currently, there are few methods for treating 1,4-dioxane in wastewater treatment systems of wastewater treatment plants. Summary of the invention

[0006] The purpose of the present invention is to provide a device and method for treating 1,4-dioxane in waste textile wastewater, so as to effectively remove 1,4-dioxane in industrial wastewater.

[0007] In order to achieve the above-mentioned object, one aspect of the present invention provides a device for treating 1,4-dioxane in waste textile wastewater, the device comprising a homogenizing tank, an anaerobic expanded granular bed reactor (EGSB reactor), an aerobic biochemical reactor, an adsorption-biochemical co-reactor (ESAB co-reactor) and a water outlet tank connected in sequence;

[0008] The adsorption-biochemical co-synergistic reactor is filled with 1,4-dioxane degradation filler; the raw materials for preparing the 1,4-dioxane degradation filler include 1,4-dioxane degradation composite biological bacterial agent and silane modified biological zeolite carrier;

[0009] The 1,4-dioxane degradation composite biological agent comprises a 1,4-dioxane composite biological agent, a biological promoter and a biodegradable adhesive; the mass ratio of the 1,4-dioxane composite biological agent, the biological promoter and the biodegradable adhesive is 100:(5-10):(1-5);

[0010] A granular sludge nucleating agent is added into the anaerobic expanded granular bed reactor.

[0011] Another aspect of the present invention provides a method for treating 1,4-dioxane in waste textile wastewater, using the above-mentioned device for treating 1,4-dioxane in waste textile wastewater, the method comprising:

[0012] (1) The wastewater enters the homogenization tank, is homogenized and pH adjusted, and then enters the anaerobic expanded particle bed reactor for anaerobic reaction;

[0013] (2) the anaerobic biochemical effluent of the anaerobic expanded granular bed reactor enters the aerobic biochemical reactor to undergo aerobic biochemical reaction;

[0014] (3) the effluent from the aerobic biochemical reactor enters the adsorption-biochemical co-reactor to perform adsorption-coupled biochemical reaction;

[0015] (4) The effluent from the adsorption-biochemical co-reactor enters the effluent pool and is discharged.

[0016] The technical solution of the present invention has the following beneficial effects:

[0017] (1) The present invention is directed to waste textile wastewater and can effectively remove organic pollutants in the wastewater.

[0018] (2) In the present invention, the 1,4-dioxane degrading filler can specifically adsorb and degrade 1,4-dioxane. The biozeolite carrier has a large capacity for adsorbing 1,4-dioxane and can effectively degrade 1,4-dioxane through specific microorganisms, thereby achieving pollutant removal.

[0019] (3) In the present invention, the ESAB co-reactor specifically removes 1,4-dioxane, occupies a small area and has high efficiency.

[0020] (4) The anaerobic biochemical reaction efficiency of the present invention is high, the granular sludge is not easy to break, and part of the 1,4-dioxane can be specifically opened and degraded.

[0021] (5) The process of the present invention has a short reaction flow, a compact device structure, and saves reagent addition, which can reduce the investment cost and operating cost of the reaction device.

[0022] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

[0024] Figure 1 A schematic structural diagram of a device for treating 1,4-dioxane in waste textile wastewater according to an embodiment of the present invention is shown.

[0025] Description of reference numerals:

[0026] 1. Homogenizing tank, 2. EGSB reactor, 3. Aerobic biochemical reactor, 4. ESAB co-reactor, 5. Outlet pool, 6. Micro liquid tank DETAILED DESCRIPTION

[0027] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0028] One aspect of the present invention provides a device for treating 1,4-dioxane in waste textile wastewater, the device comprising a homogenizing tank, an anaerobic expanded granular bed reactor (EGSB reactor), an aerobic biochemical reactor, an adsorption-biochemical co-reactor (ESAB co-reactor) and a water outlet tank connected in sequence;

[0029] The ESAB adsorption-biochemical co-synergistic reactor is filled with 1,4-dioxane degradation filler; the raw materials for preparing the 1,4-dioxane degradation filler include 1,4-dioxane degradation composite biological bacterial agent and silane modified biological zeolite carrier;

[0030] The 1,4-dioxane degradation composite biological agent comprises a 1,4-dioxane composite biological agent, a biological promoter and a biodegradable adhesive; the mass ratio of the 1,4-dioxane composite biological agent, the biological promoter and the biodegradable adhesive is 100:(5-10):(1-5);

[0031] A granular sludge nucleating agent is added into the anaerobic expanded granular bed reactor.

[0032] According to the present invention, preferably, the 1,4-dioxane composite biological agent comprises 1,4-dioxane degrading bacteria and 1,4-dioxane cometabolism degrading bacteria, and the mass ratio of the 1,4-dioxane degrading bacteria to the 1,4-dioxane cometabolism degrading bacteria is (5-8):1;

[0033] The 1,4-dioxane degrading bacteria include Pseudonocardiadioxanivorans, Mycobacterium sp. and Xanthobacter flavus, and the mass ratio of the Pseudonocardiadioxanivorans, Mycobacterium sp. and Xanthobacter flavus is (2-4):(2-4):1;

[0034] The 1,4-dioxane co-metabolism degradation bacteria include Pseudonocardia sp. and Mycobacterium sp., and the mass ratio of Pseudonocardia sp. to Mycobacterium sp. is (1-2):1.

[0035] In the present invention, preferably, in the 1,4-dioxane degrading bacteria, the dioxane-loving Pseudonocardia is Pseudonocardia dioxanivorans CB1190, the mycobacterium is Mycobacterium sp.D11, and the yellow bacterium is Xanthobacter flavusDT8;

[0036] In the 1,4-dioxane cometabolic degrading bacteria, the Pseudonocardia is Pseudonocardia sp. K1, and the Mycobacterium is Mycobacterium sp. JOB5.

[0037] In the present invention, the above strains can be obtained by commercial purchase or laboratory cultivation and separation; for example, they can be obtained by the following method: enrichment culture and separation and purification of activated sludge in a culture medium with 1,4-dioxane as a substrate. Each liter of inorganic salt culture medium contains: Na2HPO4·12H2O (4.5g), K2HPO4 (1.0g), NH4Cl (1.5g), MgSO4·7H2O (0.2g), CaCl2·2H2O (0.03g) and trace element solution 1 mL. Each liter of rare element solution contains: MnSO4·H2O (0.1g), Na2MoO4·2H2O (0.02g), H3BO3 (0.014g), FeSO4·7H2O (1.0g), ZnSO4·7H2O (0.1g), CuSO4·5H2O (0.02g), and COCl2·6H2O (0.02g). The concentration of 1,4-dioxane added is 50-100mg / L. The specific culture and separation and purification conditions in the above method are all conventional conditions in the art.

[0038] According to the present invention, preferably, the biological promoter includes yeast extract, sodium pyruvate, n-butanol, casein peptone, EDTA, MgSO4 and KH2PO4, and the mass ratio is (4-6):(2-4):(2-4):(4-6):(3-5):(0.4-0.6):(0.4-0.6);

[0039] The biodegradable adhesive is carboxymethyl chitosan adhesive or starch adhesive.

[0040] According to the present invention, preferably, the silane-modified biozeolite carrier is prepared by a preparation method comprising the following steps:

[0041] (1) stirring and mixing an aqueous solution of tetrapropylammonium hydroxide (TPAOH) and tetrabutyl titanate (TBOT), then adding tetraethyl orthosilicate (TEOS) and stirring, and then adding polystyrene microspheres and stirring to obtain a synthetic solution;

[0042] (2) placing the synthetic liquid in a dynamic homogeneous reactor for reaction, and then centrifuging, washing, drying, and calcining to obtain a biozeolite carrier;

[0043] (3) Immersing the biozeolite carrier in a silane coupling agent-ethanol aqueous solution, and then drying the immersed biozeolite carrier to obtain the silane-modified biozeolite carrier.

[0044] According to the present invention, preferably, in step (1), the mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 20-30%;

[0045] The materials of the synthetic liquid are configured so that in the synthetic liquid: the Si / Ti molar ratio is 20-60:1, preferably 30-50:1; the TPAOH / Si molar ratio is 0.03-0.07:1, preferably 0.04-0.06:1;

[0046] The mass dosage of the polystyrene microspheres (PS microspheres) is 0.05-0.1wt% based on the total weight of the synthetic liquid;

[0047] In step (2), the reaction temperature is 150-180°C and the reaction time is 1-2 days; the calcination temperature is 500-600°C and the reaction time is 5-8 hours;

[0048] In step (3), the immersion time is 0.5-1h; the concentration of the silane coupling agent in the silane coupling agent-ethanol aqueous solution is 2-10g / L, preferably 4-8g / L; and the mass concentration of the ethanol aqueous solution is 60-80%.

[0049] Polystyrene microspheres (PS microspheres) were purchased from Zhongke Keyou.

[0050] According to the present invention, preferably, the 1,4-dioxane degradable filler is prepared by a preparation method comprising the following steps: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradable composite biological bacterial agent, and then drying the impregnated silane-modified biological zeolite carrier to obtain the 1,4-dioxane degradable filler;

[0051] Preferably, the immersion time is 0.5-1 h; the drying temperature is 25-35° C. and the drying time is 2-3 h; and the particle size of the 1,4-dioxane degradable filler is 1.5-3 mm.

[0052] According to the present invention, preferably, the adsorption-biochemical co-reactor comprises a water and gas distribution unit, a support layer and a 1,4-dioxane degradation filler layer;

[0053] Wherein, the water and gas distribution unit is arranged at the bottom of the adsorption-biochemical co-synergistic reactor, a supporting layer is arranged at the top, and a 1,4-dioxane degradation filler layer is arranged on the supporting layer;

[0054] The volume filling ratio of the 1,4-dioxane degradation filler layer is 50-80%;

[0055] The water and air distribution unit comprises a filter plate and a filter head arranged on the filter plate;

[0056] Preferably, the supporting layer is a graded gravel layer, and the particle size of the graded gravel used is 6-15 mm.

[0057] In the present invention, preferably, the shell of the adsorption-biochemical co-reactor is a cylindrical structure and is placed vertically.

[0058] According to the present invention, preferably, the granular sludge nucleating agent comprises F2O3 and CeO2, and the mass ratio of F2O3 to CeO2 is 3-5:1;

[0059] The mass dosage of the granular sludge nucleating agent is 0.1-0.5% of the inoculated sludge;

[0060] The particle size of the granular sludge nucleating agent is 50-100 μm, and the particle size of the formed granular sludge is 0.5-3 mm.

[0061] According to the present invention, preferably, the anaerobic expanded granular bed reactor comprises a micro-liquid tank, which is respectively connected to the outlet pipeline of the homogenizing tank and the bottom inlet of the anaerobic expanded granular bed reactor; the micro-liquid in the micro-liquid tank is merged with the outlet water of the homogenizing tank and then enters the anaerobic expanded granular bed reactor;

[0062] Preferably, the microliquid comprises: EDTA 4000-5000 mg / L, CaCl2 200-400 mg / L, MgSO4 250-400 mg / L, KH2PO4 400-600 mg / L, NiCl2·6H2O 0.05-0.2 mg / L, H3BO4 8-15 mg / L, ZnSO4·7H2O150-300 mg / L, CuSO4·5H2O 150-300 mg / L, CoCl2·6H2O 100-200 mg / L, and MnCl2·4H2O 200-400 mg / L.

[0063] In the present invention, the dosage concentration of each component in the microliquid is calculated based on the total volume of the microliquid, for example, MgSO4 250-400 mg / L means that each liter of microliquid contains 250-400 mg MgSO4.

[0064] According to the present invention, preferably, the aerobic reactor is an MBR reactor, the pore size of the ultrafiltration membrane in the MBR reactor is 0.1-0.3 μm, and the material of the ultrafiltration membrane is a hollow fiber membrane.

[0065] Another aspect of the present invention provides a method for treating 1,4-dioxane in waste textile wastewater, using the above-mentioned device for treating 1,4-dioxane in waste textile wastewater, the method comprising:

[0066] (1) The wastewater enters the homogenization tank, is homogenized and pH adjusted, and then enters the anaerobic expanded particle bed reactor for anaerobic reaction;

[0067] (2) the anaerobic biochemical effluent of the anaerobic expanded granular bed reactor enters the aerobic biochemical reactor to undergo aerobic biochemical reaction;

[0068] (3) the effluent from the aerobic biochemical reactor enters the adsorption-biochemical co-reactor to perform adsorption-coupled biochemical reaction;

[0069] (4) The effluent from the adsorption-biochemical co-reactor enters the effluent pool and is discharged.

[0070] In the present invention, the treatment of 1,4-dioxane in waste textile wastewater requires biochemical pretreatment in advance, and then enters the adsorption-biochemical co-synergistic reactor to achieve an ideal treatment effect, which is specifically achieved through the following process flow:

[0071] Waste textile wastewater enters the high-efficiency anaerobic reactor through a lifting pump, where most of the organic matter is removed through anaerobic biochemical reactions, and large-molecule organic matter is decomposed into small-molecule organic matter, thereby improving the biodegradability of the effluent; the effluent from the high-efficiency anaerobic reactor enters the aerobic reactor, where the organic pollutants in the wastewater are degraded through aerobic biochemical reactions; 1,4-dioxane is difficult to degrade through conventional biochemical degradation, so it enters the adsorption-biochemical co-reactor with the effluent from the aerobic reactor. On the one hand, the biological zeolite carrier in the reactor can quickly enrich 1,4-dioxane in the water, and 1,4-dioxane can provide a carbon source for the loaded functional bacteria through desorption and other methods to achieve complete mineralization of pollutants and regeneration of adsorbents, thereby reducing the cost of remediation; on the other hand, the suitable surface and pore structure of the zeolite carrier can provide a good growth environment for functional bacteria, and the slow-release factors can promote the reproduction of microorganisms, better adapt to adverse environments and water impact, and treat 1,4-dioxane in a targeted manner.

[0072] According to the present invention, preferably, in step (1), the pH is adjusted to 7.0-8.5;

[0073] The height-to-diameter ratio of the EGSB reactor is 8-20:1, preferably 10-15:1; the hydraulic retention time is 1-5h, preferably 2-6h; the reflux ratio is 8-20:1, preferably 10-15:1; the feed load is 15-25kg / m 3 ·d;

[0074] In step (2), the temperature of the aerobic biochemical reactor is 25-38° C., and the hydraulic retention time is 1-5 h.

[0075] According to the present invention, preferably, the anaerobic expanded granular bed reactor comprises a micro-liquid tank, and the micro-liquid tank is respectively connected to the water outlet pipeline of the homogenization tank and the bottom inlet of the anaerobic expanded granular bed reactor;

[0076] In step (1), the wastewater enters the homogenization tank, and after homogenization and pH adjustment, the effluent from the homogenization tank merges with the micro-liquid from the micro-liquid tank and enters the anaerobic expanded particle bed reactor for anaerobic reaction.

[0077] The present invention is further described below by examples:

[0078] Detection method: COD analysis in water samples was performed according to GB / T 11914-1989 (potassium dichromate method). 1,4-dioxane in water samples was determined by liquid-liquid extraction-gas chromatography-mass spectrometry, the extraction sample volume was 50mL-5L, and the detection limit of 1,4-dioxane was 0.05mg / L (50μg / L).

[0079] In the following examples and comparative examples: Pseudonocardia dioxanivorans CB1190, Mycobacterium sp.D11, Xanthobacter flavusDT8, Pseudonocardia sp.K1 and Mycobacterium sp.JOB5 were obtained by the following method: enrichment culture and separation and purification of activated sludge in a culture medium with 1,4-dioxane as a substrate. Each liter of inorganic salt culture medium contains: Na2HPO4·12H2O (4.5g), K2HPO4 (1.0g), NH4Cl (1.5g), MgSO4·7H2O (0.2g), CaCl2·2H2O (0.03g) and 1 mL of trace element solution. Each liter of rare element solution contains: MnSO4·H2O (0.1g), Na2MoO4·2H2O (0.02g), H3BO3 (0.014g), FeSO4·7H2O (1.0g), ZnSO4·7H2O (0.1g), CuSO4·5H2O (0.02g), and COCl2·6H2O (0.02g). The concentration of 1,4-dioxane added is 50-100mg / L.

[0080] The yeast extract and casein peptone used were purchased from Beijing Aoboxing Company;

[0081] The carboxymethyl chitosan adhesive used was purchased from Aladdin Company;

[0082] The silane coupling agent used in preparing the silane coupling agent-ethanol aqueous solution is kh550, which was purchased from Shanghai Yuanye Biotechnology;

[0083] The polystyrene microspheres used were purchased from Zhongke Keyou.

[0084] Example 1

[0085] like Figure 1 The present embodiment provides a device for treating 1,4-dioxane in waste textile wastewater, which includes a homogenizing tank 1, an EGSB reactor 2, an aerobic biochemical reactor 3, an adsorption-biochemical co-reactor (ESAB co-reactor 4) and an outlet pool 5 connected in sequence; specifically, wastewater enters the EGSB reactor 2 from the bottom through a feed pump from the homogenizing tank 1; the outlet of the EGSB reactor 2 is connected to the inlet of the aerobic reactor through a pipeline; the effluent from the aerobic reactor is pumped to the ESAB co-reactor 4; the outlet of the ESAB co-reactor 4 is connected to the inlet of the outlet pool 5 through a pipeline; the effluent from the ESAB co-reactor 4 meets the discharge standards.

[0086] The adsorption-biochemical co-reactor comprises a water-gas distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer; the water-gas distribution unit is arranged at the bottom of the adsorption-biochemical co-reactor, the supporting layer is arranged at the top, and the 1,4-dioxane degradation filler layer is arranged on the supporting layer; the volume filling ratio of the 1,4-dioxane degradation filler layer is 65%; the water-gas distribution unit comprises a filter plate and a filter head arranged on the filter plate; the supporting layer is a graded gravel layer, and the particle size of the graded gravel used is 6-15 mm.

[0087] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-synergistic reactor is a 1,4-dioxane degradation filler; the raw materials for preparing the 1,4-dioxane degradation filler include a 1,4-dioxane degradation composite biological bacterial agent and a silane-modified biological zeolite carrier; the specific preparation method includes: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradation composite biological bacterial agent, and then drying the impregnated silane-modified biological zeolite carrier at 30°C for 2h to obtain the 1,4-dioxane degradation filler; the immersion time is 0.8h; the particle size of the 1,4-dioxane degradation filler is 1.5-2.5mm.

[0088] The 1,4-dioxane degradation composite biological agent comprises a 1,4-dioxane composite biological agent, a biological promoter and a biodegradable adhesive; the mass ratio of the 1,4-dioxane composite biological agent, the biological promoter and the biodegradable adhesive is 100:8:2;

[0089] The 1,4-dioxane composite biological agent includes 1,4-dioxane degrading bacteria and 1,4-dioxane cometabolism degrading bacteria, and the mass ratio of the 1,4-dioxane degrading bacteria to the 1,4-dioxane cometabolism degrading bacteria is 5:1; the 1,4-dioxane degrading bacteria includes Pseudonocardia dioxanivorans CB1190, Mycobacterium sp.D11 and Xanthobacter flavusDT8, and the mass ratio of Pseudonocardia dioxanivorans CB1190, Mycobacteriumsp.D11 and Xanthobacter flavus DT8 is 2:2:1; the 1,4-dioxane cometabolism degrading bacteria includes Pseudonocardia sp.K1 and Mycobacterium sp.JOB5, and the mass ratio of Pseudonocardia sp.K1 to Mycobacterium sp.JOB5 is 1:1;

[0090] The biological promoter comprises yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4, and the mass ratio of yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4 is 5:3:3:5:4:0.5:0.5;

[0091] The biodegradable adhesive is carboxymethyl chitosan adhesive.

[0092] The silane-modified biological zeolite carrier is prepared by a preparation method comprising the following steps: first, tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred in a beaker for 15 minutes, tetrabutyl titanate (TBOT) is added dropwise and suspended and stirred for 1 hour, then tetraethyl orthosilicate (TEOS) is added and stirred for 1.5 hours, and then polystyrene microspheres are added and stirred for 4 hours, the synthetic liquid is placed in a dynamic homogeneous reactor at 160° C. for reaction for 1 day, after centrifugation, washing and drying, calcined in a muffle furnace at 550° C. for 6 hours to obtain the biological zeolite carrier; the biological zeolite carrier is immersed in a silane coupling agent-ethanol aqueous solution, and the immersion time is 0.8 hours; then the immersed biological zeolite carrier is dried to obtain the silane-modified biological zeolite carrier; in the silane coupling agent-ethanol aqueous solution, the concentration of the silane coupling agent is 4 g / L; the mass concentration of the ethanol aqueous solution is 70%;

[0093] The mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 25%; the materials of the synthetic liquid are configured so that the molar ratio of Si / Ti in the synthetic liquid is 30:1, and the molar ratio of TPAOH / Si is 0.04:1; the mass dosage of the polystyrene microspheres is 0.05wt% based on the total weight of the synthetic liquid; the particle size of the polystyrene microspheres is 30nm,

[0094] Wherein, a granular sludge nucleating agent is added into the EGSB reactor 2. The granular sludge nucleating agent includes F2O3 and CeO2, and the mass ratio of F2O3 to CeO2 is 4:1; the mass addition amount of the granular sludge nucleating agent is 0.15% of the inoculated sludge amount; the particle size of the granular sludge nucleating agent is 55 μm, and the particle size of the formed granular sludge is 0.5-3 mm;

[0095] The EGSB reactor 2 includes a micro-liquid tank 6, which is respectively connected to the outlet pipeline of the homogenizing tank 1 and the bottom inlet of the anaerobic expanded granular bed reactor 2, so that the micro-liquid in the micro-liquid tank 6 merges with the outlet water of the homogenizing tank 1 and enters the anaerobic expanded granular bed reactor 2;

[0096] The microliquid comprises: 5000 mg / L EDTA, 300 mg / L CaCl2, 350 mg / L MgSO4, 500 mg / L KH2PO4, 0.1 mg / L NiCl2·6H2O, 10 mg / L H3BO4, 200 mg / L ZnSO4·7H2O, 200 mg / L CuSO4·5H2O, 150 mg / L CoCl2·6H2O, and 300 mg / L MnCl2·4H2O.

[0097] The aerobic reactor is an MBR reactor, the pore size of the ultrafiltration membrane in the MBR reactor is 0.2 μm, and the material of the ultrafiltration membrane is a hollow fiber membrane.

[0098] In this embodiment, the COD of the waste textile wastewater to be treated is 1564 mg / L, and the 1,4-dioxane is 10.2 mg / L.

[0099] Using the above device, the specific processing method is as follows:

[0100] (1) Wastewater enters the homogenization tank 1 for homogenization and adjustment of pH to 8.0. The effluent from the homogenization tank 1 merges with the micro-liquid in the micro-liquid tank 6 and enters the EGSB reactor 2 from the bottom through a feed pump for high-efficiency anaerobic reaction. The EGSB has a height-to-diameter ratio of 10, a hydraulic retention time of 2 h, a reflux ratio of 11, and a feed load of 16 kg / m 3 ·d;

[0101] (2) The anaerobic biochemical effluent of the EGSB reactor 2 is separated into three phases at the top, and the effluent flows into the aerobic biochemical reactor 3 by gravity from the upper outlet to undergo aerobic biochemical reaction, thereby removing most of the organic matter in the wastewater; the temperature of the aerobic reactor is 29° C., and the hydraulic retention time is 2 h.

[0102] (3) the effluent from the aerobic biochemical reactor 3 enters the reactor from the bottom of the ESAB co-reactor 4 through a pump to perform adsorption coupled biochemical reaction;

[0103] (4) The effluent from the adsorption-biochemical co-reactor flows by gravity into the effluent pool 5 and is discharged in compliance with the standards. The effluent COD concentration after treatment is 32 mg / L, and the 1,4-dioxane concentration is 51.6 μg / L.

[0104] Example 2

[0105] The differences between the device for treating 1,4-dioxane in waste textile wastewater of this embodiment and embodiment 1 are as follows:

[0106] The adsorption-biochemical co-reactor comprises a water-gas distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer; the water-gas distribution unit is arranged at the bottom of the adsorption-biochemical co-reactor, the supporting layer is arranged at the top, and the 1,4-dioxane degradation filler layer is arranged on the supporting layer; the volume filling ratio of the 1,4-dioxane degradation filler layer is 70%; the water-gas distribution unit comprises a filter plate and a filter head arranged on the filter plate; the supporting layer is a graded gravel layer, and the particle size of the graded gravel used is 6-15 mm.

[0107] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-reactor is a 1,4-dioxane degradation filler; the raw materials for preparing the 1,4-dioxane degradation filler include a 1,4-dioxane degradation composite biological bacterial agent and a silane-modified biological zeolite carrier; the specific preparation method includes: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradation composite biological bacterial agent, and then drying the impregnated silane-modified biological zeolite carrier at 30°C for 2.5h to obtain the 1,4-dioxane degradation filler; the immersion time is 0.5h; the particle size of the 1,4-dioxane degradation filler is 2-3mm.

[0108] The 1,4-dioxane degradation composite biological agent comprises a 1,4-dioxane composite biological agent, a biological promoter and a biodegradable adhesive; the mass ratio of the 1,4-dioxane composite biological agent, the biological promoter and the biodegradable adhesive is 100:7:3;

[0109] The 1,4-dioxane composite biological agent includes 1,4-dioxane degrading bacteria and 1,4-dioxane cometabolism degrading bacteria, and the mass ratio of the 1,4-dioxane degrading bacteria to the 1,4-dioxane cometabolism degrading bacteria is 5:1; the 1,4-dioxane degrading bacteria includes Pseudonocardia dioxanivorans CB1190, Mycobacterium sp.D11 and Xanthobacter flavus DT8, and the mass ratio of Pseudonocardia dioxanivorans CB1190, Mycobacterium sp.D11 and Xanthobacter flavus DT8 is 3:2:1; the 1,4-dioxane cometabolism degrading bacteria includes Pseudonocardia sp.K1 and Mycobacterium sp.JOB5, and the mass ratio of Pseudonocardia sp.K1 to Mycobacterium sp.JOB5 is 1.5:1;

[0110] The biological promoter comprises yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4, and the mass ratio of yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4 is 4:2:2:4:4:0.4:0.4;

[0111] The biodegradable adhesive is carboxymethyl chitosan adhesive.

[0112] The silane-modified biological zeolite carrier is prepared by a preparation method comprising the following steps: first, tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred in a beaker for 15 minutes, tetrabutyl titanate (TBOT) is added dropwise and suspended and stirred for 1 hour, then tetraethyl orthosilicate (TEOS) is added and stirred for 1.5 hours, and then polystyrene microspheres are added and stirred for 4 hours, the synthetic liquid is placed in a dynamic homogeneous reactor at 160° C. for reaction for 1 day, after centrifugation, washing and drying, calcined in a muffle furnace at 550° C. for 6 hours to obtain the biological zeolite carrier; the biological zeolite carrier is immersed in a silane coupling agent-ethanol aqueous solution, and the immersion time is 0.8 hours; then the immersed biological zeolite carrier is dried to obtain the silane-modified biological zeolite carrier; in the silane coupling agent-ethanol aqueous solution, the concentration of the silane coupling agent is 5 g / L; the mass concentration of the ethanol aqueous solution is 65%;

[0113] The mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 25%; the materials of the synthetic liquid are configured so that the molar ratio of Si / Ti in the synthetic liquid is 35:1, and the molar ratio of TPAOH / Si is 0.04:1; the mass dosage of the polystyrene microspheres is 0.06wt% based on the total weight of the synthetic liquid; the particle size of the polystyrene microspheres is 30nm;

[0114] Wherein, a granular sludge nucleating agent is added into the EGSB reactor 2. The granular sludge nucleating agent includes F2O3 and CeO2, and the mass ratio of F2O3 to CeO2 is 4:1; the mass addition amount of the granular sludge nucleating agent is 0.2% of the inoculated sludge amount; the particle size of the granular sludge nucleating agent is 70 μm, and the particle size of the formed granular sludge is 0.5-3 mm;

[0115] The microliquid comprises: EDTA 4000mg / L, CaCl2 200mg / L, MgSO4 250mg / L, KH2PO4 400mg / L, NiCl2·6H2O 0.05mg / L, H3BO4 8mg / L, ZnSO4·7H2O 150mg / L, CuSO4·5H2O 150mg / L, CoCl2·6H2O 100mg / L, and MnCl2·4H2O 200mg / L.

[0116] In this embodiment, the COD of the waste textile wastewater to be treated is 3240 mg / L, and the 1,4-dioxane is 32.9 mg / L.

[0117] Using the above device, the specific processing method is as follows:

[0118] (1) Wastewater enters the homogenization tank 1 for homogenization and adjustment of pH to 8.2. The effluent from the homogenization tank 1 merges with the micro-liquid in the micro-liquid tank 6 and enters the EGSB reactor 2 from the bottom through a feed pump for high-efficiency anaerobic reaction. The EGSB has a height-to-diameter ratio of 12, a hydraulic retention time of 3 h, a reflux ratio of 12, and a feed load of 18 kg / m 3 ·d;

[0119] (2) The anaerobic biochemical effluent of the EGSB reactor 2 is separated into three phases at the top, and the effluent flows into the aerobic biochemical reactor 3 from the upper outlet to undergo aerobic biochemical reaction, thereby removing most of the organic matter in the wastewater; the temperature of the aerobic reactor is 30° C., and the hydraulic retention time is 2 h.

[0120] (3) the effluent from the aerobic biochemical reactor 3 enters the reactor from the bottom of the ESAB co-reactor 4 through a pump to perform adsorption coupled biochemical reaction;

[0121] (4) The effluent from the adsorption-biochemical co-reactor flows by gravity into the effluent pool 5 and is discharged in compliance with the standards. The effluent COD concentration after treatment is 39 mg / L, and the 1,4-dioxane concentration is 55.3 μg / L.

[0122] Example 3

[0123] The differences between the device for treating 1,4-dioxane in waste textile wastewater of this embodiment and embodiment 1 are as follows:

[0124] The adsorption-biochemical co-reactor comprises a water-gas distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer; the water-gas distribution unit is arranged at the bottom of the adsorption-biochemical co-reactor, the supporting layer is arranged at the top, and the 1,4-dioxane degradation filler layer is arranged on the supporting layer; the volume filling ratio of the 1,4-dioxane degradation filler layer is 70%; the water-gas distribution unit comprises a filter plate and a filter head arranged on the filter plate; the supporting layer is a graded gravel layer, and the particle size of the graded gravel used is 6-15 mm.

[0125] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-reactor is a 1,4-dioxane degradation filler; the raw materials for preparing the 1,4-dioxane degradation filler include a 1,4-dioxane degradation composite biological bacterial agent and a silane-modified biological zeolite carrier; the specific preparation method includes: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradation composite biological bacterial agent, and then drying the impregnated silane-modified biological zeolite carrier at 30°C for 3h to obtain the 1,4-dioxane degradation filler; the immersion time is 1h; the particle size of the 1,4-dioxane degradation filler is 2-3mm.

[0126] The 1,4-dioxane degradation composite biological agent comprises a 1,4-dioxane composite biological agent, a biological promoter and a biodegradable adhesive; the mass ratio of the 1,4-dioxane composite biological agent, the biological promoter and the biodegradable adhesive is 100:8:4;

[0127] The 1,4-dioxane composite biological agent includes 1,4-dioxane degrading bacteria and 1,4-dioxane cometabolism degrading bacteria, and the mass ratio of the 1,4-dioxane degrading bacteria to the 1,4-dioxane cometabolism degrading bacteria is 5:1; the 1,4-dioxane degrading bacteria includes Pseudonocardia dioxanivorans CB1190, Mycobacterium sp.D11 and Xanthobacter flavusDT8, and the mass ratio of Pseudonocardia dioxanivorans CB1190, Mycobacteriumsp.D11 and Xanthobacter flavus DT8 is 3:3:1; the 1,4-dioxane cometabolism degrading bacteria includes Pseudonocardia sp.K1 and Mycobacterium sp.JOB5, and the mass ratio of Pseudonocardia sp.K1 to Mycobacterium sp.JOB5 is 2:1;

[0128] The biological promoter comprises yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4, and the mass ratio of yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4 is 6:4:4:6:5:0.6:0.6;

[0129] The biodegradable adhesive is carboxymethyl chitosan adhesive.

[0130] The silane-modified biological zeolite carrier is prepared by a preparation method comprising the following steps: first, tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred in a beaker for 15 minutes, tetrabutyl titanate (TBOT) is added dropwise and suspended and stirred for 1 hour, then tetraethyl orthosilicate (TEOS) is added and stirred for 1.5 hours, and then polystyrene microspheres are added and stirred for 4 hours, the synthetic liquid is placed in a dynamic homogeneous reactor at 160° C. for reaction for 1 day, after centrifugation, washing and drying, calcined in a muffle furnace at 550° C. for 6 hours to obtain the biological zeolite carrier; the biological zeolite carrier is immersed in a silane coupling agent-ethanol aqueous solution, and the immersion time is 0.8 hours; then the immersed biological zeolite carrier is dried to obtain the silane-modified biological zeolite carrier; in the silane coupling agent-ethanol aqueous solution, the concentration of the silane coupling agent is 6 g / L; the mass concentration of the ethanol aqueous solution is 80%;

[0131] The mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 25%; the materials of the synthetic liquid are configured so that the molar ratio of Si / Ti in the synthetic liquid is 35:1, and the molar ratio of TPAOH / Si is 0.04:1; the mass dosage of the polystyrene microspheres is 0.06wt% based on the total weight of the synthetic liquid; the particle size of the polystyrene microspheres is 30nm;

[0132] Wherein, a granular sludge nucleating agent is added into the EGSB reactor 2. The granular sludge nucleating agent includes F2O3 and CeO2, and the mass ratio of F2O3 to CeO2 is 4:1; the mass addition amount of the granular sludge nucleating agent is 0.3% of the inoculated sludge amount; the particle size of the granular sludge nucleating agent is 80 μm, and the particle size of the formed granular sludge is 0.5-3 mm;

[0133] The microliquid comprises: 5000mg / L EDTA, 300mg / L CaCl2, 400mg / L MgSO4, 600mg / L KH2PO4, 0.2mg / L NiCl2·6H2O, 15mg / L H3BO4, 300mg / L ZnSO4·7H2O, 300mg / L CuSO4·5H2O, 200mg / L CoCl2·6H2O, and 400mg / L MnCl2·4H2O.

[0134] In this embodiment, the COD of the waste textile wastewater to be treated is 5720 mg / L, and the 1,4-dioxane is 65.7 mg / L.

[0135] Using the above device, the specific processing method is as follows:

[0136] (1) Wastewater enters the homogenization tank 1 for homogenization and adjustment of pH to 7.8. The effluent from the homogenization tank 1 merges with the micro-liquid in the micro-liquid tank 6 and enters the EGSB reactor 2 from the bottom through a feed pump for high-efficiency anaerobic reaction. The EGSB has a height-to-diameter ratio of 13, a hydraulic retention time of 2 h, a reflux ratio of 13, and a feed load of 20 kg / m 3 ·d;

[0137] (2) The anaerobic biochemical effluent of the EGSB reactor 2 is separated into three phases at the top, and the effluent flows into the aerobic biochemical reactor 3 by gravity from the upper outlet to undergo aerobic biochemical reaction, thereby removing most of the organic matter in the wastewater; the temperature of the aerobic reactor is 33° C., and the hydraulic retention time is 3 h.

[0138] (3) the effluent from the aerobic biochemical reactor 3 enters the reactor from the bottom of the ESAB co-reactor 4 through a pump to perform adsorption coupled biochemical reaction;

[0139] (4) The effluent from the adsorption-biochemical co-reactor flows by gravity into the effluent pool 5 and is discharged in compliance with the standards. The effluent COD concentration after treatment is 47 mg / L and the 1,4-dioxane concentration is 59.1 μg / L.

[0140] Example 4

[0141] The differences between the device for treating 1,4-dioxane in waste textile wastewater of this embodiment and embodiment 1 are as follows:

[0142] The adsorption-biochemical co-reactor comprises a water-gas distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer; the water-gas distribution unit is arranged at the bottom of the adsorption-biochemical co-reactor, the supporting layer is arranged at the top, and the 1,4-dioxane degradation filler layer is arranged on the supporting layer; the volume filling ratio of the 1,4-dioxane degradation filler layer is 75%; the water-gas distribution unit comprises a filter plate and a filter head arranged on the filter plate; the supporting layer is a graded gravel layer, and the particle size of the graded gravel used is 6-15 mm.

[0143] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-synergistic reactor is a 1,4-dioxane degradation filler; the raw materials for preparing the 1,4-dioxane degradation filler include a 1,4-dioxane degradation composite biological bacterial agent and a silane-modified biological zeolite carrier; the specific preparation method includes: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradation composite biological bacterial agent, and then drying the impregnated silane-modified biological zeolite carrier at 30°C for 3h to obtain the 1,4-dioxane degradation filler; the immersion time is 1h; the particle size of the 1,4-dioxane degradation filler is 1.8-2.8mm.

[0144] The 1,4-dioxane degradation composite biological agent comprises a 1,4-dioxane composite biological agent, a biological promoter and a biodegradable adhesive; the mass ratio of the 1,4-dioxane composite biological agent, the biological promoter and the biodegradable adhesive is 100:10:5;

[0145] The 1,4-dioxane composite biological agent includes 1,4-dioxane degrading bacteria and 1,4-dioxane cometabolism degrading bacteria, and the mass ratio of the 1,4-dioxane degrading bacteria to the 1,4-dioxane cometabolism degrading bacteria is 7:1; the 1,4-dioxane degrading bacteria includes Pseudonocardia dioxanivorans CB1190, Mycobacterium sp.D11 and Xanthobacter flavusDT8, and the mass ratio of Pseudonocardia dioxanivorans CB1190, Mycobacteriumsp.D11 and Xanthobacter flavus DT8 is 4:3:1; the 1,4-dioxane cometabolism degrading bacteria includes Pseudonocardia sp.K1 and Mycobacterium sp.JOB5, and the mass ratio of Pseudonocardia sp.K1 to Mycobacterium sp.JOB5 is 1:1;

[0146] The biological promoter comprises yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4, and the mass ratio of yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4 is 5:3:3:6:4:0.6:0.6;

[0147] The biodegradable adhesive is carboxymethyl chitosan adhesive.

[0148] The silane-modified biological zeolite carrier is prepared by a preparation method comprising the following steps: first, tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred in a beaker for 15 minutes, tetrabutyl titanate (TBOT) is added dropwise and suspended and stirred for 1 hour, then tetraethyl orthosilicate (TEOS) is added and stirred for 1.5 hours, and then polystyrene microspheres are added and stirred for 4 hours, the synthetic liquid is placed in a dynamic homogeneous reactor at 160° C. for reaction for 1 day, after centrifugation, washing and drying, calcined in a muffle furnace at 550° C. for 6 hours to obtain the biological zeolite carrier; the biological zeolite carrier is immersed in a silane coupling agent-ethanol aqueous solution, and the immersion time is 0.8 hours; then the immersed biological zeolite carrier is dried to obtain the silane-modified biological zeolite carrier; in the silane coupling agent-ethanol aqueous solution, the concentration of the silane coupling agent is 8 g / L; the mass concentration of the ethanol aqueous solution is 60%;

[0149] The mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 25%; the materials of the synthetic liquid are configured so that the molar ratio of Si / Ti in the synthetic liquid is 45:1, and the molar ratio of TPAOH / Si is 0.06:1; the mass dosage of the polystyrene microspheres is 0.08wt% based on the total weight of the synthetic liquid; the particle size of the polystyrene microspheres is 30nm;

[0150] Wherein, a granular sludge nucleating agent is added into the EGSB reactor 2. The granular sludge nucleating agent includes F2O3 and CeO2, and the mass ratio of F2O3 to CeO2 is 4:1; the mass addition amount of the granular sludge nucleating agent is 0.4% of the inoculated sludge amount; the particle size of the granular sludge nucleating agent is 90 μm, and the particle size of the formed granular sludge is 0.5-3 mm;

[0151] The microliquid comprises: 5000 mg / L EDTA, 300 mg / L CaCl2, 300 mg / L MgSO4, 400 mg / L KH2PO4, 0.2 mg / L NiCl2·6H2O, 10 mg / L H3BO4, 200 mg / L ZnSO4·7H2O, 200 mg / L CuSO4·5H2O, 100 mg / L CoCl2·6H2O, and 200 mg / L MnCl2·4H2O.

[0152] In this embodiment, the COD of the waste textile wastewater to be treated is 6247 mg / L, and the 1,4-dioxane is 84.6 mg / L.

[0153] Using the above device, the specific processing method is as follows:

[0154] (1) Wastewater enters the homogenization tank 1 for homogenization and adjustment of pH to 7.5. The effluent from the homogenization tank 1 merges with the micro-liquid in the micro-liquid tank 6 and enters the EGSB reactor 2 from the bottom through a feed pump for high-efficiency anaerobic reaction. The EGSB has a height-to-diameter ratio of 15, a hydraulic retention time of 2.5 h, a reflux ratio of 14, and a feed load of 23 kg / m 3 ·d;

[0155] (2) The anaerobic biochemical effluent of the EGSB reactor 2 is separated into three phases at the top, and the effluent flows into the aerobic biochemical reactor 3 from the upper outlet to undergo aerobic biochemical reaction, thereby removing most of the organic matter in the wastewater; the temperature of the aerobic reactor is 35° C., and the hydraulic retention time is 3 h.

[0156] (3) the effluent from the aerobic biochemical reactor 3 enters the reactor from the bottom of the ESAB co-reactor 4 through a pump to perform adsorption coupled biochemical reaction;

[0157] (4) The effluent from the adsorption-biochemical co-reactor flows by gravity into the effluent pool 5 and is discharged in compliance with the discharge standards. The effluent COD concentration after treatment is 52 mg / L, and the 1,4-dioxane concentration is 58.5 μg / L.

[0158] Example 5

[0159] The differences between the device for treating 1,4-dioxane in waste textile wastewater of this embodiment and embodiment 1 are as follows:

[0160] The adsorption-biochemical co-reactor comprises a water-gas distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer; the water-gas distribution unit is arranged at the bottom of the adsorption-biochemical co-reactor, the supporting layer is arranged at the top, and the 1,4-dioxane degradation filler layer is arranged on the supporting layer; the volume filling ratio of the 1,4-dioxane degradation filler layer is 80%; the water-gas distribution unit comprises a filter plate and a filter head arranged on the filter plate; the supporting layer is a graded gravel layer, and the particle size of the graded gravel used is 6-15 mm.

[0161] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-synergistic reactor is a 1,4-dioxane degradation filler; the raw materials for preparing the 1,4-dioxane degradation filler include a 1,4-dioxane degradation composite biological bacterial agent and a silane-modified biological zeolite carrier; the specific preparation method includes: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradation composite biological bacterial agent, and then drying the impregnated silane-modified biological zeolite carrier at 30°C for 2h to obtain the 1,4-dioxane degradation filler; the immersion time is 0.5h; the particle size of the 1,4-dioxane degradation filler is 1.5-2.5mm.

[0162] The 1,4-dioxane degradation composite biological agent comprises a 1,4-dioxane composite biological agent, a biological promoter and a biodegradable adhesive; the mass ratio of the 1,4-dioxane composite biological agent, the biological promoter and the biodegradable adhesive is 100:5:1;

[0163] The 1,4-dioxane composite biological agent includes 1,4-dioxane degrading bacteria and 1,4-dioxane cometabolism degrading bacteria, and the mass ratio of the 1,4-dioxane degrading bacteria to the 1,4-dioxane cometabolism degrading bacteria is 7:1; the 1,4-dioxane degrading bacteria includes Pseudonocardia dioxanivorans CB1190, Mycobacterium sp.D11 and Xanthobacter flavusDT8, and the mass ratio of Pseudonocardia dioxanivorans CB1190, Mycobacterium sp.D11 and Xanthobacter flavusDT8 is 4:4:1; the 1,4-dioxane cometabolism degrading bacteria includes Pseudonocardia sp.K1 and Mycobacterium sp.JOB5, and the mass ratio of Pseudonocardia sp.K1 to Mycobacterium sp.JOB5 is 2:1;

[0164] The biological promoter comprises yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4, and the mass ratio of yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4 is 6:4:4:5:4:0.5:0.5;

[0165] The biodegradable adhesive is carboxymethyl chitosan adhesive.

[0166] The silane-modified biological zeolite carrier is prepared by a preparation method comprising the following steps: first, tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred in a beaker for 15 minutes, tetrabutyl titanate (TBOT) is added dropwise and suspended and stirred for 1 hour, then tetraethyl orthosilicate (TEOS) is added and stirred for 1.5 hours, and then polystyrene microspheres are added and stirred for 4 hours, the synthetic liquid is placed in a dynamic homogeneous reactor at 160° C. for reaction for 1 day, after centrifugation, washing and drying, calcined in a muffle furnace at 550° C. for 6 hours to obtain the biological zeolite carrier; the biological zeolite carrier is immersed in a silane coupling agent-ethanol aqueous solution, and the immersion time is 0.8 hours; then the immersed biological zeolite carrier is dried to obtain the silane-modified biological zeolite carrier; in the silane coupling agent-ethanol aqueous solution, the concentration of the silane coupling agent is 10 g / L; the mass concentration of the ethanol aqueous solution is 80%;

[0167] The mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 25%; the materials of the synthetic liquid are configured so that the molar ratio of Si / Ti in the synthetic liquid is 48:1, and the molar ratio of TPAOH / Si is 0.07:1; the mass dosage of the polystyrene microspheres is 0.1wt% based on the total weight of the synthetic liquid; the particle size of the polystyrene microspheres is 30nm;

[0168] Wherein, a granular sludge nucleating agent is added into the EGSB reactor 2. The granular sludge nucleating agent includes F2O3 and CeO2, and the mass ratio of F2O3 to CeO2 is 4:1; the mass addition amount of the granular sludge nucleating agent is 0.4% of the inoculated sludge amount; the particle size of the granular sludge nucleating agent is 90 μm, and the particle size of the formed granular sludge is 0.5-3 mm;

[0169] The microliquid comprises: EDTA 5000mg / L, CaCl2 200mg / L, MgSO4 400mg / L, KH2PO4 500mg / L, NiCl2·6H2O 0.2mg / L, H3BO4 12mg / L, ZnSO4·7H2O 200mg / L, CuSO4·5H2O 200mg / L, CoCl2·6H2O 150mg / L, and MnCl2·4H2O 200mg / L.

[0170] In this embodiment, the COD of the waste textile wastewater to be treated is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L.

[0171] Using the above device, the specific processing method is as follows:

[0172] (1) Wastewater enters the homogenization tank 1 for homogenization and adjustment of pH to 7.3. The effluent from the homogenization tank 1 merges with the micro-liquid in the micro-liquid tank 6 and enters the EGSB reactor 2 from the bottom through a feed pump for high-efficiency anaerobic reaction. The EGSB has a height-to-diameter ratio of 18, a hydraulic retention time of 3 h, a reflux ratio of 15, and a feed load of 25 kg / m 3 ·d;

[0173] (2) The anaerobic biochemical effluent of the EGSB reactor 2 is separated into three phases at the top, and the effluent flows into the aerobic biochemical reactor 3 by gravity from the upper outlet to undergo aerobic biochemical reaction, thereby removing most of the organic matter in the wastewater; the temperature of the aerobic reactor is 25° C., and the hydraulic retention time is 4 h.

[0174] (3) the effluent from the aerobic biochemical reactor 3 enters the reactor from the bottom of the ESAB co-reactor 4 through a pump to perform adsorption coupled biochemical reaction;

[0175] (4) The effluent from the adsorption-biochemical co-reactor flows by gravity into the effluent pool 5 and is discharged in compliance with the discharge standards. The effluent COD concentration after treatment is 58 mg / L, and the 1,4-dioxane concentration is 61.2 μg / L.

[0176] Comparative Example 1

[0177] The difference between the apparatus for treating 1,4-dioxane in waste textile wastewater in this comparative example and that in Example 5 is that the ESAB co-reactor 4 does not use the silane-modified biological zeolite carrier of Example 5, but replaces it with a common zeolite with a particle size of 1-2 mm;

[0178] The COD of the waste textile wastewater to be treated in this comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device of this comparative example is used for treatment, and the specific treatment method and process parameters are the same as those in Example 5;

[0179] The comparative example has low treatment efficiency for COD and 1,4-dioxane. After treatment, the COD concentration of the effluent is 220 mg / L, and the 1,4-dioxane concentration is 1029 μg / L.

[0180] Comparative Example 2

[0181] The difference between the apparatus for treating 1,4-dioxane in waste textile wastewater in this comparative example and that in Example 5 is that the ESAB co-reactor 4 does not use the 1,4-dioxane composite biological agent of Example 5, but replaces it with biological activated sludge from the secondary sedimentation tank of the municipal sewage treatment plant;

[0182] The COD of the waste textile wastewater to be treated in this comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device of this comparative example is used for treatment, and the specific treatment method and process parameters are the same as those in Example 5;

[0183] The comparative example has low treatment efficiency for COD and 1,4-dioxane. The COD concentration of the effluent after treatment is 268 mg / L, and the 1,4-dioxane concentration is 1496 μg / L.

[0184] Comparative Example 3

[0185] The difference between the apparatus for treating 1,4-dioxane in waste textile wastewater in this comparative example and that in Example 5 is that no biological promoter is added in the preparation of the 1,4-dioxane composite biological bacterial agent used;

[0186] The COD of the waste textile wastewater to be treated in this comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device of this comparative example is used for treatment, and the specific treatment method and process parameters are the same as those in Example 5;

[0187] In this comparative example, the biofilm start-up period of ESAB co-reactor 4 was extended by 1 time than normal, and the treatment efficiency of COD and 1,4-dioxane was low. The COD concentration of the effluent after treatment was 183 mg / L, and the 1,4-dioxane concentration was 963 μg / L.

[0188] Comparative Example 4

[0189] The difference between the apparatus for treating 1,4-dioxane in waste textile wastewater in this comparative example and that in Example 5 is that the aerobic biochemical reactor 3 is not used, and the anaerobic effluent directly enters the ESAB co-reactor 4;

[0190] The COD of the waste textile wastewater to be treated in this comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device of this comparative example is used for treatment, and the specific treatment method is different from that of Example 5 only in that the anaerobic biochemical effluent of the EGSB reactor 2 is subjected to three-phase separation at the top to remove the good oxidation reaction, and the effluent flows into the ESAB co-cooperative reactor 4 by gravity from the upper outlet; the rest is the same as Example 5;

[0191] In this comparative example, the packing layer of the ESAB reactor is easily clogged, the backwashing frequency increases, the biological packing cannot function normally, and the COD and 1,4-dioxane treatment efficiency is low. The COD concentration of the effluent after treatment is 512 mg / L, and the 1,4-dioxane concentration is 1743 μg / L.

[0192] Comparative Example 5

[0193] The difference between the apparatus for treating 1,4-dioxane in waste textile wastewater in this comparative example and that in Example 5 is that the EGSB reactor 2 is replaced by an upflow sludge blanket (UASB);

[0194] The wastewater to be treated in this comparative example has a COD of 8465 mg / L and a 1,4-dioxane of 103.5 mg / L. The device of this comparative example is used for treatment, and the specific treatment method is different from that of Example 5 only in that: Step (1) the wastewater enters the homogenization tank 1, is homogenized and the pH is adjusted to 7.3, and enters the upflow sludge bed from the bottom through the feed pump for anaerobic reaction, the temperature is 20-30°C, and the hydraulic retention time is 10h; the rest is the same as Example 5;

[0195] In this comparative example, the anaerobic biochemical efficiency is low, which affects the aerobic biochemical efficiency and the ESAB treatment effect. The treatment efficiency of COD and 1,4-dioxane is low. The COD concentration of the effluent after treatment is 629 mg / L, and the 1,4-dioxane concentration is 698 μg / L.

[0196] Comparative Example 6

[0197] The difference between the apparatus for treating 1,4-dioxane in waste textile wastewater in this comparative example and that in Example 5 is that no granular sludge nucleating agent is added to the EGSB reactor 2;

[0198] The COD of the waste textile wastewater to be treated in this comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device of this comparative example is used for treatment, and the specific treatment method and process parameters are the same as those in Example 5;

[0199] In this comparative example, the granular sludge was easily broken by impact, and the treatment efficiency of COD and 1,4-dioxane was low. The COD concentration of the effluent after treatment was 318 mg / L, and the 1,4-dioxane concentration was 547 μg / L.

[0200] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A device for treating 1,4-dioxane in waste textile wastewater, characterized in that: The device comprises a homogenizing tank, an anaerobic expanded granular bed reactor, an aerobic biochemical reactor, an adsorption-biochemical co-synergistic reactor and a water outlet pool which are connected in sequence; The adsorption-biochemical co-synergistic reactor is filled with 1,4-dioxane degradation filler; the raw materials for preparing the 1,4-dioxane degradation filler include 1,4-dioxane degradation composite biological bacterial agent and silane modified biological zeolite carrier; The 1,4-dioxane degradation composite biological agent comprises a 1,4-dioxane composite biological agent, a biological promoter and a biodegradable adhesive; the mass ratio of the 1,4-dioxane composite biological agent, the biological promoter and the biodegradable adhesive is 100:(5-10):(1-5); A granular sludge nucleating agent is added into the anaerobic expanded granular bed reactor.

2. The device according to claim 1, wherein: The 1,4-dioxane composite biological agent comprises 1,4-dioxane degrading bacteria and 1,4-dioxane cometabolism degrading bacteria, and the mass ratio of the 1,4-dioxane degrading bacteria to the 1,4-dioxane cometabolism degrading bacteria is (5-8):1; The 1,4-dioxane degrading bacteria include Pseudonocardiadioxanivorans, Mycobacterium sp. and Xanthobacter flavus, and the mass ratio of the Pseudonocardiadioxanivorans, Mycobacterium sp. and Xanthobacter flavus is (2-4):(2-4):1; The 1,4-dioxane co-metabolism degradation bacteria include Pseudonocardia sp. and Mycobacterium sp., and the mass ratio of Pseudonocardia sp. to Mycobacterium sp. is (1-2):

1.

3. The device according to claim 1, wherein: The biological promoter includes yeast extract, sodium pyruvate, n-butanol, casein peptone, EDTA, MgSO4 and KH2PO4, and the mass ratio is (4-6):(2-4):(2-4):(4-6):(3-5):(0.4-0.6):(0.4-0.6); The biodegradable adhesive is carboxymethyl chitosan adhesive or starch adhesive.

4. The device according to claim 1, wherein: The silane-modified biozeolite carrier is prepared by a preparation method comprising the following steps: (1) stirring and mixing an aqueous solution of tetrapropylammonium hydroxide and tetrabutyl titanate, then adding ethyl orthosilicate and stirring, and then adding polystyrene microspheres and stirring to obtain a synthetic solution; (2) placing the synthetic liquid in a dynamic homogeneous reactor for reaction, and then centrifuging, washing, drying, and calcining to obtain a biozeolite carrier; (3) Immersing the biozeolite carrier in a silane coupling agent-ethanol aqueous solution, and then drying the immersed biozeolite carrier to obtain the silane-modified biozeolite carrier.

5. The device according to claim 4, wherein: In step (1), the mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 20-30%; The materials of the synthetic liquid are configured so that in the synthetic liquid: the Si / Ti molar ratio is 20-60:1, preferably 30-50:1; the TPAOH / Si molar ratio is 0.03-0.07:1, preferably 0.04-0.06:1; The mass dosage of the polystyrene microspheres is 0.05-0.1wt% based on the total weight of the synthetic liquid; In step (2), the reaction temperature is 150-180°C and the reaction time is 1-2 days; the calcination temperature is 500-600°C and the reaction time is 5-8 hours; In step (3), the immersion time is 0.5-1h; the concentration of the silane coupling agent in the silane coupling agent-ethanol aqueous solution is 2-10g / L, preferably 4-8g / L; and the mass concentration of the ethanol aqueous solution is 60-80%.

6. The device according to claim 1, wherein: The 1,4-dioxane degradable filler is prepared by a preparation method comprising the following steps: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradable composite biological bacterial agent, and then drying the impregnated silane-modified biological zeolite carrier to obtain the 1,4-dioxane degradable filler; Preferably, the immersion time is 0.5-1 h; the drying temperature is 25-35° C. and the drying time is 2-3 h; and the particle size of the 1,4-dioxane degradable filler is 1.5-3 mm.

7. The device according to claim 1, wherein: The adsorption-biochemical co-synergistic reactor comprises a water and gas distribution unit, a support layer and a 1,4-dioxane degradation filler layer; Wherein, the water and gas distribution unit is arranged at the bottom of the adsorption-biochemical co-synergistic reactor, a supporting layer is arranged at the top, and a 1,4-dioxane degradation filler layer is arranged on the supporting layer; The volume filling ratio of the 1,4-dioxane degradation filler layer is 50-80%; The water and air distribution unit comprises a filter plate and a filter head arranged on the filter plate; Preferably, the supporting layer is a graded gravel layer, and the particle size of the graded gravel used is 6-15 mm.

8. The device according to claim 1, wherein: The granular sludge nucleating agent includes F2O3 and CeO2, and the mass ratio of F2O3 to CeO2 is 3-5:1; The mass dosage of the granular sludge nucleating agent is 0.1-0.5% of the inoculated sludge; The particle size of the granular sludge nucleating agent is 50-100 μm, and the particle size of the formed granular sludge is 0.5-3 mm.

9. The device according to claim 1, wherein: The anaerobic expanded granular bed reactor comprises a micro-liquid tank, which is respectively connected to the outlet pipeline of the homogenizing tank and the bottom inlet of the anaerobic expanded granular bed reactor; the micro-liquid in the micro-liquid tank is merged with the outlet water of the homogenizing tank and then enters the anaerobic expanded granular bed reactor; Preferably, the microliquid comprises: EDTA 4000-5000 mg / L, CaCl2 200-400 mg / L, MgSO4 250-400 mg / L, KH2PO4 400-600 mg / L, NiCl2·6H2O 0.05-0.2 mg / L, H3BO4 8-15 mg / L, ZnSO4·7H2O 150-300 mg / L, CuSO4·5H2O 150-300 mg / L, CoCl2·6H2O 100-200 mg / L, and MnCl2·4H2O 200-400 mg / L.

10. The device according to claim 1, wherein: The aerobic reactor is an MBR reactor. The pore size of the ultrafiltration membrane in the MBR reactor is 0.1-0.3 μm, and the material of the ultrafiltration membrane is a hollow fiber membrane.

11. A method for treating 1,4-dioxane in waste textile wastewater, using the device for treating 1,4-dioxane in waste textile wastewater according to any one of claims 1 to 10, characterized in that: The method includes: (1) The wastewater enters the homogenization tank, is homogenized and pH adjusted, and then enters the anaerobic expanded particle bed reactor for anaerobic reaction; (2) the anaerobic biochemical effluent of the anaerobic expanded granular bed reactor enters the aerobic biochemical reactor to undergo aerobic biochemical reaction; (3) the effluent from the aerobic biochemical reactor enters the adsorption-biochemical co-reactor to perform adsorption-coupled biochemical reaction; (4) The effluent from the adsorption-biochemical co-reactor enters the effluent pool and is discharged.

12. The method according to claim 11, wherein: In step (1), the pH is adjusted to 7.0-8.5; The height-to-diameter ratio of the EGSB reactor is 8-20:1, preferably 10-15:1; the hydraulic retention time is 1-5h, preferably 2-6h; the reflux ratio is 8-20:1, preferably 10-15:1; the feed load is 15-25kg / m 3 ·d; In step (2), the temperature of the aerobic biochemical reactor is 25-38° C., and the hydraulic retention time is 1-5 h.

13. The method according to claim 11, wherein: The anaerobic expanded granular bed reactor comprises a micro-liquid tank, which is respectively connected to the water outlet pipeline of the homogenization tank and the bottom inlet of the anaerobic expanded granular bed reactor; In step (1), the wastewater enters the homogenization tank, and after homogenization and pH adjustment, the effluent from the homogenization tank merges with the micro-liquid from the micro-liquid tank and enters the anaerobic expanded particle bed reactor for anaerobic reaction.

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