A device and method for treating 1,4-dioxane in waste spinning wastewater

Abstract

The application belongs to the field of chemical industry and environmental protection technology, and discloses a device and method for treating 1,4-dioxane in waste spinning wastewater, which comprises a homogenizing tank, an anaerobic expanded granular bed reactor, an aerobic biochemical reactor, an adsorption-biochemical co-collaborative reactor and a water outlet tank connected in sequence; the adsorption-biochemical co-collaborative reactor is filled with 1,4-dioxane degradation filler; the raw material for preparing the 1,4-dioxane degradation filler comprises 1,4-dioxane degradation composite biological inoculant and silane modified biological zeolite carrier; the 1,4-dioxane degradation composite biological inoculant comprises 1,4-dioxane composite biological inoculant, biological accelerant and biodegradable adhesive; the mass ratio of the 1,4-dioxane composite biological inoculant, the biological accelerant and the biodegradable adhesive is 100:(5-10):(1-5); the granular sludge nucleating agent is added into the anaerobic expanded granular bed reactor; and the application can effectively remove organic pollutants in waste spinning wastewater.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical industry and environmental protection, and more particularly to a device and method for treating 1,4-dioxane in waste spinning wastewater. BACKGROUND

[0002] The resource utilization of waste polyester textiles can effectively realize the recycling of waste polyester, which is an environmentally friendly and renewable process path. The tail gas generated by each process device in the waste polyester textile regeneration and depolymerization process needs to be treated by a tail gas washing tower to meet the emission standard. The wastewater from the tail gas washing tower contains high-concentration organic matter and has complex components. Due to the formation of by-products in the production process, the wastewater also contains high-concentration 1,4-dioxane. 1,4-dioxane is an organic compound, also known as dioxane or 1,4-dioxane, which is a colorless liquid with a slight fragrance. It is slightly toxic and has irritating effects on the skin, eyes, and respiratory system, and may cause damage to the liver, kidneys, and nervous system, and even death in acute poisoning.

[0003] CN 106865733 A discloses a method for removing 1,4-dioxane from water bodies by persulfate oxidation, but this invention uses persulfate as an oxidizing agent, and the reaction process needs to be heated, which consumes a large amount of reagent and has high cost.

[0004] CN 104710019 B discloses a method for treating chlorinated hydrocarbons / dioxanes by zero-valent iron-activated sludge coupling, which removes dioxanes by adding zero-valent iron in activated sludge under anaerobic conditions, but this invention requires a large amount of zero-valent iron, and the treatment cost of the remaining activated sludge is high.

[0005] Currently, there are few methods for treating 1,4-dioxane in waste polyester process wastewater treatment systems. SUMMARY

[0006] The purpose of the present application is to provide a device and method for treating 1,4-dioxane in waste spinning wastewater, which can effectively remove 1,4-dioxane in industrial wastewater.

[0007] To achieve the above-mentioned purpose, one aspect of the present application provides a device for treating 1,4-dioxane in waste spinning wastewater, which comprises a homogenizing tank, an anaerobic expanded granular bed reactor (EGSB reactor), an aerobic biochemical reactor, an adsorption-biochemical co-coupling reactor (ESAB co-coupling reactor), and a water outlet pool connected in sequence;

[0008] The adsorption-biochemical co-coupling 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 inoculant 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; and 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] The granular sludge nucleating agent is added into the anaerobic expanded granular bed reactor.

[0011] Another aspect of the present application provides a method for treating 1,4-dioxane in waste spinning wastewater, which adopts the device for treating 1,4-dioxane in waste spinning wastewater, and the method comprises the following steps:

[0012] (1) After the wastewater enters the homogenizing tank and is subjected to homogenization and pH adjustment, the wastewater enters the anaerobic expanded granular bed reactor and is subjected to anaerobic reaction.

[0013] (2) The anaerobically biologically treated effluent of the anaerobic expanded granular bed reactor enters the aerobic bioreactor and is subjected to aerobic biochemical reaction.

[0014] (3) The effluent of the aerobic bioreactor enters the adsorption-biochemical co-coupling reactor and is subjected to adsorption-coupled biochemical reaction.

[0015] (4) The effluent of the adsorption-biochemical co-coupling reactor enters the effluent tank and is discharged.

[0016] The technical scheme of the present application has the following beneficial effects:

[0017] (1) The present application can effectively remove organic pollutants in waste spinning wastewater.

[0018] (2) In the present application, the 1,4-dioxane degradation filler can adsorb and degrade 1,4-dioxane, the bio-zeolite carrier has a large capacity for adsorbing 1,4-dioxane, and the specific microorganism can effectively degrade 1,4-dioxane to remove pollutants.

[0019] (3) In the present application, the ESAB co-coupling reactor can specifically remove 1,4-dioxane, has a small occupied area and high efficiency.

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

[0021] (5) The process reaction flow of the present application is short, the device structure is compact, the addition of reagents is saved, and the investment cost and operation cost of the reaction device can be reduced.

[0022] Other features and advantages of the present application will be described in detail in the following specific embodiment part. BRIEF DESCRIPTION OF DRAWINGS

[0023] The exemplary embodiments of the present application will be described in more detail by making reference to the accompanying drawings.

[0024] Figure 1 A schematic structural diagram of a device for treating 1,4-dioxane in waste spinning sewage according to one embodiment of the present application is shown.

[0025] Legend of reference signs:

[0026] 1, homogenizing tank, 2, EGSB reactor, 3, aerobic biochemical reactor, 4, ESAB co-collaborative reactor, 5, effluent tank, 6, micro-liquid tank DETAILED DESCRIPTION

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

[0028] One aspect of the present application provides a device for treating 1,4-dioxane in waste spinning sewage, which comprises a homogenizing tank, an anaerobic expanded granular bed reactor (EGSB reactor), an aerobic biochemical reactor, an adsorption-biochemical co-collaborative reactor (ESAB co-collaborative reactor) and an effluent tank connected in sequence;

[0029] wherein the ESAB adsorption-biochemical co-collaborative 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 inoculant and silane modified biological zeolite carrier;

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

[0031] The anaerobic expanded granular bed reactor is added with a granular sludge nucleating agent.

[0032] According to the present application, preferably, the 1,4-dioxane composite biological inoculant includes 1,4-dioxane degrading bacteria and 1,4-dioxane co-metabolic degrading bacteria, and the mass ratio of the 1,4-dioxane degrading bacteria and 1,4-dioxane co-metabolic degrading bacteria is (5-8):1;

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

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

[0035] In the present application, preferably, in the 1,4-dioxane degrading bacteria, the Pseudonocardia dioxanivorans is CB1190, the Mycobacterium sp. is D11, and the Xanthobacter flavus is DT8.

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

[0037] In the present application, the above-mentioned strains can be obtained by commercial purchase or laboratory culture and isolation; for example, the above-mentioned strains can be obtained by the following method: through enrichment culture and isolation 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 (4.5 g), K2HPO4 (1.0 g), NH4Cl (1.5 g), MgSO4·7H2O (0.2 g), CaCl2·2H2O (0.03 g), and trace element solution 1 mL. Each liter of trace element solution contains MnSO4·H2O (0.1 g), Na2MoO4·2H2O (0.02 g), H3BO3 (0.014 g), FeSO4·7H2O (1.0 g), ZnSO4·7H2O (0.1 g), CuSO4·5H2O (0.02 g), and COCl2·6H2O (0.02 g). The concentration of 1,4-dioxane is 50-100 mg / L. The specific culture and isolation and purification conditions in the above-mentioned method are all conventional conditions in the art.

[0038] According to the application, preferably, the biological promoter comprises 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 application, preferably, the silane-modified biological zeolite carrier is prepared by a preparation method comprising the following steps:

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

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

[0043] (3) immersing the biological zeolite carrier in a silane coupling agent-ethanol aqueous solution, and then drying the biological zeolite carrier subjected to the immersion treatment to obtain the silane-modified biological zeolite carrier.

[0044] According to the application, preferably, in step (1), the mass concentration of the aqueous solution of tetrapropyl ammonium hydroxide is 20-30%.

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

[0046] The mass addition amount of the polystyrene microspheres (PS microspheres) is 0.05-0.1 wt% based on the total weight of the synthesis liquid.

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

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

[0049] The polystyrene microspheres (PS microspheres) are purchased from Zhongke Keyou.

[0050] According to the present application, preferably, the 1,4-dioxane degradation filler is prepared by a preparation method comprising the following steps: immersing the silane-modified biozeolite carrier in the 1,4-dioxane degradation composite biological inoculant, and then drying the silane-modified biozeolite carrier after the impregnation treatment to obtain the 1,4-dioxane degradation filler.

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

[0052] According to the present application, preferably, the adsorption-biochemical co-collaborative reactor comprises a water and air distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer.

[0053] Preferably, the adsorption-biochemical co-collaborative reactor is provided with the water and air distribution unit at the bottom, and the supporting layer at the upper part, and the 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 6-15mm.

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

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

[0059] The mass addition amount of the granular sludge nucleating agent is 0.1-0.5% of the amount of inoculated sludge.

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

[0061] According to the present application, preferably, the anaerobic expanded granular bed reactor comprises a micro-liquid tank, which is respectively connected with the effluent 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 combined with the effluent of the homogenizing tank and then enters the anaerobic expanded granular bed reactor.

[0062] Preferably, the micro-liquid 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, MnCl2·4H2O 200-400 mg / L.

[0063] In the present application, the concentration of each component in the micro-liquid is based on the total volume of the micro-liquid, for example, MgSO4 250-400 mg / L means that 250-400 mg of MgSO4 is contained per liter of micro-liquid.

[0064] According to the present application, 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 application provides a method for treating 1,4-dioxane in waste spinning wastewater, which adopts the device for treating 1,4-dioxane in waste spinning wastewater described above, and the method comprises:

[0066] (1) the wastewater enters the homogenizing tank, is subjected to homogenization and pH adjustment, and then enters the anaerobic expanded granular bed reactor to perform anaerobic reaction;

[0067] (2) the anaerobically biologically treated effluent of the anaerobic expanded granular bed reactor enters the aerobic bioreactor to perform aerobic biochemical reaction;

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

[0069] (4) the effluent of the adsorption-biochemical co-coupled reactor enters the effluent tank and is discharged.

[0070] In the present application, the biochemical pretreatment of 1,4-dioxane in waste spinning wastewater is performed in advance, and then the wastewater enters the adsorption-biochemical co-coupled reactor to achieve ideal treatment effect, which is realized by the following process flow:

[0071] The waste spinning sewage enters the high-efficiency anaerobic reactor through a lifting pump, most of the organic matters are removed through an anaerobic biochemical reaction, macromolecular organic matters are decomposed into small molecular organic matters, and the biodegradability of the effluent is improved; the effluent of the high-efficiency anaerobic reactor enters the aerobic reactor, and the organic pollutants in the wastewater are degraded through an aerobic biochemical reaction; 1,4-dioxane is difficult to be degraded through conventional biochemical degradation, and enters the adsorption-biochemical co-coupling reactor with the effluent of the aerobic reactor; the biological zeolite carrier in the reactor can enrich 1,4-dioxane in water on one hand, and the 1,4-dioxane provides a carbon source for the functional bacteria in the form of desorption and the like to achieve complete mineralization of the pollutants and regeneration of the adsorbent, so that the remediation cost is reduced; on the other hand, the suitable surface and pore structure of the zeolite carrier can provide a good growth environment for the functional bacteria, the factor is released to promote the reproduction of the microorganisms, the microorganisms can better adapt to the adverse environment and water inflow impact, and 1,4-dioxane is treated in a targeted manner.

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

[0073] The height-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℃, and the hydraulic retention time is 1-5h.

[0075] According to the present application, preferably, the anaerobic expanded granular bed reactor comprises a micro-liquid tank, which is connected with the effluent pipeline of the homogenizing tank and the bottom inlet of the anaerobic expanded granular bed reactor, respectively;

[0076] In step (1), the wastewater enters the homogenizing tank, and after homogenization and pH adjustment, the effluent of the homogenizing tank is combined with the micro-liquid of the micro-liquid tank and then enters the anaerobic expanded granular bed reactor for anaerobic reaction.

[0077] The present application is further illustrated by the following examples:

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

[0079] In the following examples and comparative examples: Pseudonocardia dioxanivorans CB1190, Mycobacterium sp. D11, Xanthobacter flavus DT8, Pseudonocardia sp. K1 and Mycobacterium sp. JOB5 used were obtained by the following method: enrichment culture and isolation and purification by culturing activated sludge in a culture medium with 1,4-dioxane as substrate. Each liter of inorganic salt culture medium contains: Na2HPO4·12H2O (4.5 g), K2HPO4 (1.0 g), NH4Cl (1.5 g), MgSO4·7H2O (0.2 g), CaCl2·2H2O (0.03 g) and trace element solution l mL. Each liter of trace element solution contains: MnSO4·H2O (0.1 g), Na2MoO4·2H2O (0.02 g), H3BO3 (0.014 g), FeSO4·7H2O (1.0 g), ZnSO4·7H2O (0.1 g), CuSO4·5H2O (0.02 g), and COCl2·6H2O (0.02 g). The dosage of 1,4-dioxane is 50-100 mg / 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;

[0082] The silane coupling agent used for preparing the silane coupling agent-ethanol aqueous solution was kh550, which was purchased from Shanghai Yuanye Bio.

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

[0084] Example 1

[0085] As Figure 1 described, the present embodiment provides a device for treating 1,4-dioxane in waste spinning wastewater, which comprises, in sequence, a homogenizing tank 1, an EGSB reactor 2, an aerobic biochemical reactor 3, an adsorption-biochemical co-collaborative reactor (ESAB co-collaborative reactor 4) and a water outlet tank 5. Specifically, wastewater is introduced from the bottom of the homogenizing tank 1 into the EGSB reactor 2 by a feed pump; the water outlet of the EGSB reactor 2 is connected to the inlet of the aerobic reactor by a pipeline; the water outlet of the aerobic reactor is pumped to the ESAB co-collaborative reactor 4; the outlet of the ESAB co-collaborative reactor 4 is connected to the inlet of the water outlet tank 5 by a pipeline; and the water outlet of the ESAB co-collaborative reactor 4 is discharged up to standard.

[0086] The adsorption-biochemical co-collaborative reactor comprises a water and air distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer; the water and air distribution unit is arranged at the bottom of the adsorption-biochemical co-collaborative reactor, the supporting layer is arranged at the upper portion of the adsorption-biochemical co-collaborative reactor, 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 and air distribution unit comprises a filter plate and a filter head arranged on the filter plate; and the supporting layer is a graded gravel layer, and the graded gravel used has a particle size of 6-15 mm.

[0087] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-collaborative reactor is a 1,4-dioxane degradation filler; the raw material for preparing the 1,4-dioxane degradation filler comprises a 1,4-dioxane degradation composite biological inoculant and a silane-modified biological zeolite carrier; the specific preparation method comprises the following steps: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradation composite biological inoculant, and then drying the silane-modified biological zeolite carrier subjected to the immersion treatment at 30℃ for 2h to obtain the 1,4-dioxane degradation filler; the immersion time is 0.8h; and the particle size of the 1,4-dioxane degradation filler is 1.5-2.5mm.

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

[0089] The 1,4-dioxane composite biological inoculant comprises 1,4-dioxane degradation bacteria and 1,4-dioxane co-metabolic degradation bacteria, and the mass ratio of the 1,4-dioxane degradation bacteria and the 1,4-dioxane co-metabolic degradation bacteria is 5:1; the 1,4-dioxane degradation bacteria comprises 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 2:2:1; the 1,4-dioxane co-metabolic degradation bacteria comprises Pseudonocardia sp.K1 and Mycobacterium sp.JOB5, and the mass ratio of Pseudonocardia sp.K1 and 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 the 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 a carboxymethyl chitosan adhesive.

[0092] The silane-modified bio-zeolite carrier is prepared by a preparation method comprising the following steps: firstly, mixing and stirring tetrapropyl ammonium hydroxide (TPAOH) and deionized water in a beaker for 15 min, adding titanium tetrabutoxide (TBOT) drop by drop and suspending for 1 h, then adding tetraethyl orthosilicate (TEOS) and stirring for 1.5 h, and then adding polystyrene microspheres and stirring for 4 h; the synthesis liquid is placed in a dynamic homogeneous reactor and reacted at 160℃ for 1 day; after centrifugation, washing and drying, the bio-zeolite carrier is obtained by calcining in a muffle furnace at 550℃ for 6 hours; the bio-zeolite carrier is immersed in a silane coupling agent-ethanol aqueous solution, and the immersion time is 0.8 h; then the bio-zeolite carrier after immersion treatment is dried to obtain the silane-modified bio-zeolite carrier; in the silane coupling agent-ethanol aqueous solution, the concentration of the silane coupling agent is 4 g / L; and the mass concentration of the ethanol aqueous solution is 70%.

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

[0094] The EGSB reactor 2 is provided with a granular sludge nucleating agent. The granular sludge nucleating agent comprises F2O3 and CeO2, and the mass ratio of the F2O3 and CeO2 is 4:1; the mass addition amount of the granular sludge nucleating agent is 0.15% of the amount of inoculated sludge; 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 comprises a micro-liquid tank 6, which is connected with the effluent pipeline of the homogenizing tank 1 and the bottom inlet of the anaerobic expanded granular bed reactor 2 respectively, so that the micro-liquid in the micro-liquid tank 6 is combined with the effluent of the homogenizing tank 1 and then enters the anaerobic expanded granular bed reactor 2.

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

[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] The COD of the waste spinning wastewater to be treated in the example is 1564 mg / L, and the 1,4-dioxane is 10.2 mg / L.

[0099] The specific treatment method is as follows by using the above device:

[0100] (1) The wastewater enters the homogenizing tank 1, homogenizes and adjusts the pH to 8.0, the effluent of the homogenizing tank 1 is combined with the micro liquid of the micro liquid tank 6, and then enters the EGSB reactor 2 from the bottom through the feed pump for high-efficiency anaerobic reaction; the height-diameter ratio of the EGSB is 10, the hydraulic retention time is 2 h, the reflux ratio is 11, and the feed load is 16 kg / m 3 ·d;

[0101] (2) The anaerobic biochemical effluent of the EGSB reactor 2 is subjected to three-phase separation at the top, and the effluent flows into the aerobic biochemical reactor 3 from the upper effluent port for aerobic biochemical reaction to remove most of the organic matter in the wastewater; the temperature of the aerobic reactor is 29℃, and the hydraulic retention time is 2 h.

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

[0103] (4) The effluent of the adsorption-biochemical co-coupled reactor flows into the effluent tank 5 to achieve standard discharge. The COD concentration of the treated effluent is 32 mg / L, and the 1,4-dioxane concentration is 51.6 μg / L.

[0104] Example 2

[0105] The difference between the device for treating 1,4-dioxane in waste spinning wastewater in the example and the device in example 1 is as follows:

[0106] The adsorption-biochemical co-collaborative reactor comprises a water and air distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer; the water and air distribution unit is arranged at the bottom of the adsorption-biochemical co-collaborative reactor, the supporting layer is arranged at the upper portion of the adsorption-biochemical co-collaborative reactor, 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 and air distribution unit comprises a filter plate and a filter head arranged on the filter plate; and the supporting layer is a graded gravel layer, and the graded gravel used has a particle size of 6-15 mm.

[0107] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-collaborative reactor is a 1,4-dioxane degradation filler; the raw material for preparing the 1,4-dioxane degradation filler comprises a 1,4-dioxane degradation composite biological inoculant and a silane-modified biological zeolite carrier; the specific preparation method comprises the following steps: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradation composite biological inoculant, and then drying the silane-modified biological zeolite carrier subjected to the immersion treatment at 30℃ for 2.5h to obtain the 1,4-dioxane degradation filler; the immersion time is 0.5h; and the particle size of the 1,4-dioxane degradation filler is 2-3mm.

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

[0109] The 1,4-dioxane composite biological inoculant comprises 1,4-dioxane degradation bacteria and 1,4-dioxane co-metabolic degradation bacteria, and the mass ratio of the 1,4-dioxane degradation bacteria and the 1,4-dioxane co-metabolic degradation bacteria is 5:1; the 1,4-dioxane degradation bacteria comprises 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 co-metabolic degradation bacteria comprises Pseudonocardia sp.K1 and Mycobacterium sp.JOB5, and the mass ratio of Pseudonocardia sp.K1 and 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 the 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 a carboxymethyl chitosan adhesive.

[0112] The silane-modified biozeolite carrier is prepared by a preparation method comprising the following steps: firstly, mixing and stirring tetrapropyl ammonium hydroxide (TPAOH) and deionized water in a beaker for 15 min, adding titanium tetrabutoxide (TBOT) drop by drop and suspending for 1 h, then adding tetraethyl orthosilicate (TEOS) and stirring for 1.5 h, and then adding polystyrene microspheres and stirring for 4 h; the synthesis liquid is placed in a dynamic homogeneous reactor and reacted at 160℃ for 1 day; after centrifugation, washing and drying, the biozeolite carrier is obtained by calcining at 550℃ for 6 hours in a muffle furnace; the biozeolite carrier is immersed in a silane coupling agent-ethanol aqueous solution, and the immersion time is 0.8 h; then the biozeolite carrier after immersion treatment is dried to obtain the silane-modified biozeolite carrier; in the silane coupling agent-ethanol aqueous solution, the concentration of the silane coupling agent is 5 g / L; and the mass concentration of the ethanol aqueous solution is 65%.

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

[0114] The EGSB reactor 2 is added with a granular sludge nucleating agent. The granular sludge nucleating agent comprises F2O3 and CeO2, and the mass ratio of the F2O3 and CeO2 is 4:1; the mass addition amount of the granular sludge nucleating agent is 0.2% of the amount of inoculated sludge; 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 micro liquid comprises: EDTA 4000 mg / L, CaCl2 200 mg / L, MgSO4 250 mg / L, KH2PO4 400 mg / L, NiCl2·6H2O 0.05 mg / L, H3BO4 8 mg / L, ZnSO4·7H2O 150 mg / L, CuSO4·5H2O 150 mg / L, CoCl2·6H2O 100 mg / L, and MnCl2·4H2O 200 mg / L.

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

[0117] The specific treatment method is as follows using the above device.

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

[0119] (2) The anaerobic biochemical effluent of the EGSB reactor 2 is subjected to three-phase separation at the top, and the effluent flows into the aerobic biochemical reactor 3 from the upper effluent port for aerobic biochemical reaction to remove 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 of the aerobic biochemical reactor 3 enters the reactor from the bottom of the ESAB co-coupled reactor 4 through a pump for adsorption-coupled biochemical reaction.

[0121] (4) The effluent of the adsorption-biochemical co-coupled reactor flows into the effluent tank 5 for discharge. The COD concentration of the treated effluent is 39 mg / L, and the 1,4-dioxane concentration is 55.3 μg / L.

[0122] Example 3

[0123] The difference between the device for treating 1,4-dioxane in waste spinning wastewater in this embodiment and that in Example 1 is as follows.

[0124] The adsorption-biochemical co-coupled reactor comprises a water and air distribution unit, a supporting layer, and a 1,4-dioxane degradation filler layer. The water and air distribution unit is arranged at the bottom of the adsorption-biochemical co-coupled reactor, and the supporting layer is arranged at the upper portion. 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 and air 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 graded gravel used has a particle size of 6-15 mm.

[0125] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-coupled reactor is a 1,4-dioxane degradation filler; the raw material for preparing the 1,4-dioxane degradation filler includes a 1,4-dioxane degradation composite biological inoculant 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 inoculant, and then drying the silane-modified biological zeolite carrier after the immersion treatment at 30 DEG C for 3 h to obtain the 1,4-dioxane degradation filler; the immersion time is 1 h; and the particle size of the 1,4-dioxane degradation filler is 2-3 mm.

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

[0127] The 1,4-dioxane composite biological inoculant includes 1,4-dioxane degradation bacteria and 1,4-dioxane co-metabolic degradation bacteria, and the mass ratio of the 1,4-dioxane degradation bacteria and the 1,4-dioxane co-metabolic degradation bacteria is 5:1; the 1,4-dioxane degradation bacteria include 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 3:3:1; the 1,4-dioxane co-metabolic degradation bacteria include Pseudonocardia sp. K1 and Mycobacterium sp. JOB5, and the mass ratio of Pseudonocardia sp. K1 and Mycobacterium sp. JOB5 is 2:1.

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

[0129] The biodegradable adhesive is a carboxymethyl chitosan adhesive.

[0130] The silane-modified biozeolite carrier is prepared by a preparation method comprising the following steps: firstly, mixing tetrapropyl ammonium hydroxide (TPAOH) and deionized water in a beaker and stirring for 15 min, then adding tetrabutyl titanate (TBOT) drop by drop and stirring for 1 h, then adding tetraethyl orthosilicate (TEOS) and stirring for 1.5 h, then adding polystyrene microspheres and stirring for 4 h, then placing the synthesis liquid in a dynamic homogeneous reactor and reacting at 160℃ for 1 day, then centrifuging, washing, drying, and calcining in a muffle furnace at 550℃ for 6 hours to obtain the biozeolite carrier; immersing the biozeolite carrier in a silane coupling agent-ethanol aqueous solution, wherein the immersion time is 0.8 h; then drying the biozeolite carrier after the immersion treatment to obtain the silane-modified biozeolite 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 tetrapropyl ammonium hydroxide is 25%; the materials for preparing the synthesis liquid are configured such that in the synthesis liquid, the molar ratio of Si / Ti is 35:1, and the molar ratio of TPAOH / Si is 0.04:1; the mass addition amount of the polystyrene microspheres is 0.06 wt% based on the total weight of the synthesis liquid; the particle size of the polystyrene microspheres is 30 nm;

[0132] The EGSB reactor 2 is added with a granular sludge nucleating agent. The granular sludge nucleating agent comprises F2O3 and CeO2, and the mass ratio of the F2O3 and CeO2 is 4:1; the mass addition amount of the granular sludge nucleating agent is 0.3% of the amount of the inoculated sludge; 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 micro-liquid comprises: EDTA 5000 mg / L, CaCl2 300 mg / L, MgSO4 400 mg / L, KH2PO4 600 mg / L, NiCl2·6H2O 0.2 mg / L, H3BO4 15 mg / L, ZnSO4·7H2O 300 mg / L, CuSO4·5H2O 300 mg / L, CoCl2·6H2O 200 mg / L, and MnCl2·4H2O 400 mg / L.

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

[0135] The specific treatment method is as follows by using the above device:

[0136] (1) The wastewater enters the homogenizing tank 1 for homogenization and pH adjustment to 7.8. The effluent of the homogenizing tank 1 is combined with the micro-liquid of the micro-liquid tank 6 and then enters the EGSB reactor 2 from the bottom through a feed pump for high-efficiency anaerobic reaction. The EGSB has a height-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 subjected to three-phase separation at the top and then flows into the aerobic biochemical reactor 3 from the upper effluent port for aerobic biochemical reaction to remove most of the organic matter in the wastewater. The aerobic reactor has a temperature of 33℃ and a hydraulic retention time of 3 h.

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

[0139] (4) The effluent of the adsorption-biochemical co-coupled reactor flows into the effluent tank 5 for discharge. The COD concentration of the treated effluent 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 spinning wastewater in this example and example 1 are as follows:

[0142] The adsorption-biochemical co-coupled reactor comprises a water and air distribution unit, a supporting layer, and a 1,4-dioxane degradation filler layer. The water and air distribution unit is arranged at the bottom of the adsorption-biochemical co-coupled reactor, and the supporting layer is arranged at the top. 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 and air 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 graded gravel used has a particle size of 6-15 mm.

[0143] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-coupled 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 inoculant and a silane-modified biological zeolite carrier. The specific preparation method comprises the following steps: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradation composite biological inoculant, and then drying the silane-modified biological zeolite carrier treated by immersion at 30℃ for 3 h to obtain the 1,4-dioxane degradation filler. The immersion time is 1 h. The particle size of the 1,4-dioxane degradation filler is 1.8-2.8 mm.

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

[0145] The 1,4-dioxane composite microbial agent comprises 1,4-dioxane degradation bacteria and 1,4-dioxane co-metabolic degradation bacteria, and the mass ratio of the 1,4-dioxane degradation bacteria and the 1,4-dioxane co-metabolic degradation bacteria is 7:1; the 1,4-dioxane degradation bacteria comprise 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 4:3:1; the 1,4-dioxane co-metabolic degradation bacteria comprise Pseudonocardia sp. K1 and Mycobacterium sp. JOB5, and the mass ratio of Pseudonocardia sp. K1 and 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 the yeast extract, the sodium pyruvate, the n-butanol, the casein peptone acid hydrolysate, the EDTA, the MgSO4 and the KH2PO4 is 5:3:3:6:4:0.6:0.6.

[0147] The biodegradable adhesive is a carboxymethyl chitosan adhesive.

[0148] The silane-modified biozeolite carrier is prepared by a preparation method comprising the following steps: firstly, mixing and stirring tetrapropylammonium hydroxide (TPAOH) and deionized water in a beaker for 15 min, adding titanium tetrabutoxide (TBOT) drop by drop and suspending for 1 h, then adding tetraethyl orthosilicate (TEOS) and stirring for 1.5 h, and then adding polystyrene microspheres and stirring for 4 h; placing the synthesis liquid in a dynamic homogeneous reactor and reacting at 160℃ for 1 day; after centrifugation, washing and drying, calcining in a muffle furnace at 550℃ for 6 hours to obtain a biozeolite carrier; immersing the biozeolite carrier in a silane coupling agent-ethanol aqueous solution, and the immersion time is 0.8 h; then drying the biozeolite carrier after immersion treatment to obtain the silane-modified biozeolite carrier; in the silane coupling agent-ethanol aqueous solution, the concentration of the silane coupling agent is 8 g / L; and the mass concentration of the ethanol aqueous solution is 60%.

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

[0150] The EGSB reactor 2 contains a granular sludge nucleating agent. The granular sludge nucleating agent comprises F₂O₃ and CeO₂ in a mass ratio of 4:1; the mass dosage of the granular sludge nucleating agent is 0.4% of the inoculum sludge; the particle size of the granular sludge nucleating agent is 90 μm, and the resulting granular sludge has a particle size of 0.5-3 mm.

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

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

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

[0154] (1) Wastewater enters homogenizing tank 1 for homogenization and pH adjustment to 7.5. The effluent from homogenizing tank 1 is then combined with the micro-liquid from micro-liquid tank 6 and fed into EGSB reactor 2 from the bottom via a feed pump for efficient 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 biological effluent from the EGSB reactor 2 undergoes three-phase separation at the top, and the effluent flows by gravity from the upper outlet into the aerobic biological reactor 3 to carry out aerobic biological reaction, thereby removing most of the organic matter in the wastewater; the temperature of the aerobic reactor is 35℃ and the hydraulic retention time is 3h.

[0156] (3) The effluent from the aerobic biochemical reactor 3 enters the reactor from the bottom of the ESAB co-co-reactor 4 via a pump to carry out adsorption-coupled biochemical reactions;

[0157] (4) The effluent of the adsorption-biochemical co-collaborative reactor flows into the effluent pool 5 by itself, and is discharged after reaching the standard. The COD concentration of the treated effluent is 52 mg / L, and the 1,4-dioxane concentration is 58.5 μg / L.

[0158] Example 5

[0159] The difference between the device for treating 1,4-dioxane in waste spinning wastewater in this embodiment and that in Example 1 is as follows:

[0160] The adsorption-biochemical co-collaborative reactor comprises a water and air distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer. The water and air distribution unit is arranged at the bottom of the adsorption-biochemical co-collaborative reactor, and the supporting layer is arranged at the upper part. 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 and air 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 graded gravel used has a particle size of 6-15 mm.

[0161] The filler used in the 1,4-dioxane degradation filler layer of the adsorption-biochemical co-collaborative reactor is a 1,4-dioxane degradation filler. The raw material for preparing the 1,4-dioxane degradation filler comprises a 1,4-dioxane degradation composite biological inoculant and a silane-modified biological zeolite carrier. The specific preparation method comprises the following steps: immersing the silane-modified biological zeolite carrier in the 1,4-dioxane degradation composite biological inoculant, and then drying the silane-modified biological zeolite carrier after the immersion treatment at 30°C for 2 h to obtain the 1,4-dioxane degradation filler. The immersion time is 0.5 h. The particle size of the 1,4-dioxane degradation filler is 1.5-2.5 mm.

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

[0163] The 1,4-dioxane complex bio-agent includes 1,4-dioxane degrading bacteria and 1,4-dioxane co-metabolic degrading bacteria, and the mass ratio of the 1,4-dioxane degrading bacteria and the 1,4-dioxane co-metabolic degrading bacteria is 7:1; 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 4:4:1; the 1,4-dioxane co-metabolic degrading bacteria includes Pseudonocardia sp. K1 and Mycobacterium sp. JOB5, and the mass ratio of Pseudonocardia sp. K1 and Mycobacterium sp. JOB5 is 2:1;

[0164] The biological promoter includes yeast extract, sodium pyruvate, n-butanol, casein peptone acid hydrolysate, EDTA, MgSO4 and KH2PO4, and the mass ratio of the 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 a carboxymethyl chitosan adhesive.

[0166] The silane-modified bio-zeolite carrier is prepared by a preparation method including the following steps: first, tetrapropyl ammonium hydroxide (TPAOH) is mixed with deionized water in a beaker and stirred for 15 min, tetrabutyl titanate (TBOT) is added dropwise and stirred for 1 h, then tetraethyl orthosilicate (TEOS) is added and stirred for 1.5 h, and polystyrene microspheres are added and stirred for 4 h, the synthesis liquid is placed in a dynamic homogeneous reactor and reacted at 160℃ for 1 day, after centrifugation, washing and drying, the bio-zeolite carrier is obtained by calcining in a muffle furnace at 550℃ for 6 hours; the bio-zeolite carrier is immersed in a silane coupling agent-ethanol aqueous solution, and the immersion time is 0.8 h; then the bio-zeolite carrier after the immersion treatment is dried to obtain the silane-modified bio-zeolite carrier; in the silane coupling agent-ethanol aqueous solution, the concentration of the silane coupling agent is 10 g / L; and the mass concentration of the ethanol aqueous solution is 80%;

[0167] The mass concentration of the aqueous solution of the tetrapropyl ammonium hydroxide is 25%; each material for configuring the synthesis solution is configured so that in the synthesis solution: the molar ratio of Si / Ti is 48:1, the molar ratio of TPAOH / Si is 0.07:1; the mass addition amount of the polystyrene microspheres is 0.1wt% based on the total weight of the synthesis solution; and the particle size of the polystyrene microspheres is 30nm;

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

[0169] The micro-liquid 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, MnCl2·4H2O 200mg / L.

[0170] The COD of the waste spinning wastewater to be treated in the example is 8465mg / L, and the 1,4-dioxane is 103.5mg / L.

[0171] The specific treatment method is as follows by using the above device:

[0172] (1) The wastewater enters the homogenizing tank 1 to perform homogenization and adjust the pH to 7.3. The effluent of the homogenizing tank 1 and the micro-liquid of the micro-liquid tank 6 are combined and then enter the EGSB reactor 2 from the bottom through a feed pump to perform high-efficiency anaerobic reaction. The height-diameter ratio of the EGSB is 18, the hydraulic retention time is 3h, the reflux ratio is 15, and the feed load is 25kg / m 3 ·d;

[0173] (2) The anaerobic biochemical effluent of the EGSB reactor 2 is subjected to three-phase separation at the top, and the effluent is self-flowed into the aerobic biochemical reactor 3 from the upper effluent port to perform aerobic biochemical reaction to remove most of the organic matters in the wastewater. The temperature of the aerobic reactor is 25℃, and the hydraulic retention time is 4h.

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

[0175] (4) The effluent from the adsorption-biochemical co-coupled reactor flows into the effluent tank 5 by itself, and is discharged after reaching the standard. The COD concentration of the effluent after treatment is 58 mg / L, and the 1,4-dioxane concentration is 61.2 μg / L.

[0176] Comparative Example 1

[0177] The only difference between the device for treating 1,4-dioxane in waste spinning wastewater in this comparative example and that in Example 5 is that the silane-modified biological zeolite carrier in the ESAB co-coupled reactor 4 in Example 5 is replaced by ordinary zeolite with a particle size of 1-2 mm.

[0178] The COD of the waste spinning wastewater to be treated in this comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device in 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 treatment efficiency of COD and 1,4-dioxane in this comparative example is low, and the COD concentration of the effluent after treatment is 220 mg / L, and the 1,4-dioxane concentration is 1029 μg / L.

[0180] Comparative Example 2

[0181] The only difference between the device for treating 1,4-dioxane in waste spinning wastewater in this comparative example and that in Example 5 is that the 1,4-dioxane composite biological agent in the ESAB co-coupled reactor 4 in Example 5 is replaced by the biological activated sludge in the secondary sedimentation tank of a municipal sewage treatment plant.

[0182] The COD of the waste spinning wastewater to be treated in this comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device in 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 treatment efficiency of COD and 1,4-dioxane in this comparative example is low, and 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 only difference between the device for treating 1,4-dioxane in waste spinning wastewater in this comparative example and that in Example 5 is that the 1,4-dioxane composite biological agent used is not added with a biological promoter during preparation.

[0186] The COD of the waste spinning wastewater to be treated in this comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device in 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 the comparative example, the membrane formation start-up period of the ESAB co-coupled reactor 4 is 1 time longer than normal, and the treatment efficiency of COD and 1,4-dioxane is low, and the effluent COD concentration after treatment is 183 mg / L, and the 1,4-dioxane concentration is 963 μg / L.

[0188] Comparative Example 4

[0189] The difference between the device for treating 1,4-dioxane in waste spinning wastewater in the comparative example and example 5 is only that the aerobic biochemical reactor 3 is not used, and the anaerobic effluent directly enters the ESAB co-coupled reactor 4.

[0190] The COD of the waste spinning wastewater to be treated in the comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device of the comparative example is used for treatment, and the difference between the specific treatment method and example 5 is only that the aerobic oxidation reaction is removed, the anaerobic biochemical effluent of the EGSB reactor 2 is subjected to three-phase separation at the top, and the effluent flows into the ESAB co-coupled reactor 4 from the upper effluent port; the others are the same as example 5.

[0191] In the comparative example, the packing layer of the ESAB reactor is easy to be blocked, the backwashing frequency is increased, the biological packing cannot normally play a function, the treatment efficiency of COD and 1,4-dioxane is low, and the effluent COD concentration 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 device for treating 1,4-dioxane in waste spinning wastewater in the comparative example and example 5 is only that the EGSB reactor 2 is replaced by an upflow sludge bed (UASB).

[0194] The COD of the waste spinning wastewater to be treated in the comparative example is 8465 mg / L, and the 1,4-dioxane is 103.5 mg / L. The device of the comparative example is used for treatment, and the difference between the specific treatment method and example 5 is only that in step (1), the wastewater enters the homogenizing tank 1, is homogenized and adjusted to pH 7.3, enters the upflow sludge bed from the bottom through the feed pump, is subjected to anaerobic reaction, the temperature is 20-30°C, and the hydraulic retention time is 10 h; the others are the same as example 5.

[0195] In the comparative example, the anaerobic biochemical efficiency is low, the aerobic biochemical efficiency and the ESAB treatment effect are affected, the treatment efficiency of COD and 1,4-dioxane is low, and the effluent COD concentration 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 present comparative example and the device for treating 1,4-dioxane in waste spinning wastewater of Example 5 is that no granular sludge nucleating agent is added in the EGSB reactor 2;

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

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

[0200] The above has described various embodiments of the present application, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. An apparatus for treating 1,4-dioxane in waste spinning wastewater, characterized by, The device comprises a homogenizing tank, an anaerobic expanded granular bed reactor, an aerobic biochemical reactor, an adsorption-biochemical co-collaborative reactor and a water outlet pool connected in sequence; The adsorption-biochemical co-collaborative reactor is filled with 1,4-dioxane degradation filler; the raw material for preparing the 1,4-dioxane degradation filler comprises 1,4-dioxane degradation composite biological bacteria and a silane modified biological zeolite carrier; The 1,4-dioxane degradation composite biological bacteria comprises 1,4-dioxane composite biological bacteria, biological promoters and biodegradable adhesives; the mass ratio of the 1,4-dioxane composite biological bacteria, the biological promoters and the biodegradable adhesives is 100:(5-10):(1-5); The anaerobic expanded granular bed reactor is added with a granular sludge nucleating agent; The 1,4-dioxane composite biological bacteria comprises 1,4-dioxane degradation bacteria and 1,4-dioxane co-metabolic degradation bacteria, and the mass ratio of the 1,4-dioxane degradation bacteria and the 1,4-dioxane co-metabolic degradation bacteria is (5-8):1; The 1,4-dioxane-degrading bacteria include *Pseudomonas dioxanephila* (… Pseudonocardia dioxanivorans ), Mycobacterium ( Mycobacterium sp.) and Flavobacterium ( Xanthobacter flavus The mass ratio of the dioxane-loving pseudonocardia, mycobacteria, and flavobacterium is (2-4):(2-4):

1. The 1,4-dioxane co-metabolic degrading bacteria include Nocardia (… Pseudonocardia sp.) and mycobacteria ( Mycobacterium sp.), the mass ratio of the pseudonocardia to mycobacteria is (1-2):1; The silane modified biological zeolite 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 stirring and adding tetraethyl orthosilicate, and then stirring and adding polystyrene microspheres to obtain a synthesis liquid; (2) placing the synthesis liquid in a dynamic homogeneous reactor for reaction, and then centrifuging, washing, drying and calcining to obtain a biological zeolite carrier; (3) immersing the biological zeolite carrier in a silane coupling agent-ethanol aqueous solution, and then drying the biological zeolite carrier subjected to the immersion treatment to obtain the silane modified biological zeolite carrier.

2. The apparatus of claim 1, wherein, The biological promoters comprise 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 a carboxymethyl chitosan adhesive or a starch adhesive.

3. The apparatus of claim 1, wherein, In step (1), the mass concentration of the aqueous solution of tetrapropylammonium hydroxide is 20-30%; The materials for configuring the synthesis liquid are configured such that the molar ratio of Si / Ti in the synthesis liquid is 20-60:1, and the molar ratio of TPAOH / Si is 0.03-0.07:1; The mass addition amount of the polystyrene microspheres is 0.05-0.1wt% based on the total weight of the synthesis liquid; In step (2), the reaction temperature is 150-180℃, and the reaction time is 1-2 days; the calcination temperature is 500-600℃, and the calcination time is 5-8h; In step (3), the time of the immersion is 0.5-1h; the concentration of the silane coupling agent in the silane coupling agent-ethanol aqueous solution is 2-10g / L; the mass concentration of the ethanol aqueous solution is 60-80%.

4. The apparatus of claim 3, wherein, In step (1), the molar ratio of Si / Ti is 30-50:1; the molar ratio of TPAOH / Si is 0.04-0.06:1; In step (3), the concentration of the silane coupling agent in the silane coupling agent-ethanol aqueous solution is 4-8g / L.

5. The apparatus of claim 1, wherein, The 1,4-dioxane degradation filler is prepared by a preparation method comprising the following steps: immersing the silane modified biozeolite carrier in the 1,4-dioxane degradation composite bio-agent, and then drying the silane modified biozeolite carrier after the immersion treatment to obtain the 1,4-dioxane degradation filler.

6. The apparatus of claim 5, wherein, The time of the immersion is 0.5-1h; the drying temperature is 25-35℃, and the time of the drying is 2-3h; the particle size of the 1,4-dioxane degradation filler is 1.5-3mm.

7. The apparatus of claim 1, wherein, The adsorption-biochemical co-collaborative reactor comprises a water and air distribution unit, a supporting layer and a 1,4-dioxane degradation filler layer. The adsorption-biochemical co-collaborative reactor comprises a water and air distribution unit, a supporting layer and a 1,4-dioxane degradation filler 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.

8. The apparatus of claim 7, wherein, The supporting layer is a graded gravel layer, and the graded gravel used has a particle size of 6-15mm.

9. The apparatus of claim 1, wherein, The mass addition amount of the granular sludge nucleating agent is 0.1-0.5% of the amount of the inoculated sludge; The particle size of the granular sludge nucleating agent is 50-100μm, and the particle size of the formed granular sludge is 0.5-3mm.

10. The apparatus of claim 1, wherein, The micro liquid tank is connected with the effluent pipeline of the homogenizing tank and the bottom inlet of the anaerobic expanded granular bed reactor respectively; and the micro liquid in the micro liquid tank is combined with the effluent of the homogenizing tank and then enters the anaerobic expanded granular bed reactor.

11. The apparatus of claim 10, wherein, The micro liquid comprises: EDTA 4000-5000mg / L, CaCl2 200-400mg / L, MgSO4 250-400mg / L, KH2PO4 400-600mg / L, NiCl2•6H2O 0.05-0.2mg / L, H3BO4 8-15mg / L, ZnSO4•7H2O 150-300mg / L, CuSO4•5H2O 150-300mg / L, CoCl2•6H2O 100-200mg / L, MnCl2•4H2O 200-400mg / L.

12. The apparatus of claim 1, wherein, The aerobic reactor is an MBR reactor, and the pore size of the ultrafiltration membrane in the MBR reactor is 0.1-0.3μm, and the material of the ultrafiltration membrane is a hollow fiber membrane.

13. A method for treating 1,4-dioxane in waste spinning sewage, using the device for treating 1,4-dioxane in waste spinning sewage according to any one of claims 1-12, characterized in that, The method comprises: (1) the wastewater enters the homogenizing tank, is subjected to homogenization and pH adjustment, and then enters the anaerobic expanded granular bed reactor (EGSB reactor) to be subjected to anaerobic reaction; (2) The anaerobic biochemical effluent of the anaerobic expanded granular bed reactor enters the aerobic biochemical reactor for aerobic biochemical reaction; (3) The effluent of the aerobic biochemical reactor enters the adsorption-biochemical co-coupled reactor for adsorption-coupled biochemical reaction; (4) The effluent of the adsorption-biochemical co-coupled reactor enters the effluent tank for discharge.

14. The method of claim 13, wherein, In step (1), the pH is adjusted to 7.0-8.5; The EGSB reactor has a height to diameter ratio of 8-20:1; a hydraulic retention time of 1-5h; a reflux ratio of 8-20:1; a feed load of 15-25kg / m 3 • d; In step (2), the temperature of the aerobic biochemical reactor is 25-38℃, and the hydraulic retention time is 1-5h.

15. The method of claim 14, wherein, In step (1), the height-diameter ratio of the EGSB reactor is 10-15:1; the hydraulic retention time is 2-6h; and the reflux ratio is 10-15:

1.

16. The method of claim 13, wherein, The anaerobic expanded granular bed reactor comprises a micro-liquid tank, which is connected with the effluent pipeline of the homogenizing tank and the bottom inlet of the anaerobic expanded granular bed reactor, respectively; In step (1), after the wastewater enters the homogenizing tank for homogenization and pH adjustment, the effluent of the homogenizing tank is combined with the micro-liquid of the micro-liquid tank, and then enters the anaerobic expanded granular bed reactor for anaerobic reaction.

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