A grey cloth decausticizing wastewater zero discharge treatment method

Abstract

The present application relates to wastewater treatment technical field, specifically to a kind of grey cloth deblacking wastewater zero discharge treatment method;The method is added in traditional prewash, boil bleaching, one water washing, reboiling, secondary water washing, pickling and concentration process and so on process section of waste heat recovery, boil bleaching reagent recovery, reboiling reagent recovery and wastewater reuse;Through segmented processing and resource recycling, reuse, it realizes grey cloth deblacking reagent resource recycling and wastewater zero discharge.Compared with the traditional grey cloth deblacking wastewater treatment process, all process section wastewater is mixed and then treated, the present application is selectively removed interference factor by being carried out in selected process section respectively, realizes resource recycling reagent, and also effectively reduce the complexity of wastewater, significantly reduce wastewater treatment cost.In addition, the present application can effectively reduce energy loss by heat recovery.In short, the grey cloth deblacking wastewater zero discharge treatment method of the present application has good economic benefit and environmental effect, and has good industrial application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of wastewater treatment, in particular to a grey cloth de-bleaching wastewater zero discharge treatment method. BACKGROUND

[0002] Grey cloth is a kind of natural cotton cloth for printing and dyeing processing. After production, the grey cloth needs to be bleached, mainly including pre-washing, boiling and bleaching, primary washing, re-boiling, secondary washing, and neutralizing pickling. During boiling and bleaching and re-boiling, a large amount of high-temperature wastewater containing refining agents and complexing agents will be generated, which will affect the external environment if directly discharged.

[0003] In order to meet the green demand of environmental protection processing, the grey cloth de-bleaching wastewater needs to be further treated before being discharged. In view of the above problems, the current wastewater treatment process and device still treat the high COD caused by refining agents and other substances as waste, but not as resources and energy for recycling, which will lead to problems such as high energy consumption of end treatment process, large demand for reagents, and high cost.

[0004] In order to solve the above problems, the present application designs a grey cloth de-bleaching wastewater zero discharge treatment method, which aims to provide a selective treatment scheme, and regards the wastewater and pollutants in the wastewater as resource and energy carrier instead of only as pollutants, and selectively removes the key pollutants in the wastewater and recycles them to the de-bleaching process. SUMMARY

[0005] In order to achieve the above purpose, the present application designs a grey cloth de-bleaching wastewater zero discharge treatment method, and the scheme is as follows:

[0006] The traditional grey cloth de-bleaching wastewater treatment method is to make the grey cloth pass through pre-washing, boiling and bleaching, primary washing, re-boiling, secondary washing, pickling, and concentration processes in sequence for degreasing and bleaching. The present application designs a grey cloth de-bleaching wastewater zero discharge treatment method, which adds the following process section to the above process flow:

[0007] Process 1, waste heat recovery: heat exchange process is set in the boiling and bleaching and re-boiling process section to recover waste heat, and then the waste heat is transmitted to the concentration process section;

[0008] Process 2, boiling agent recovery: the wastewater generated in boiling and bleaching and the wastewater generated in primary washing are referred to as first wastewater, the first wastewater is treated based on the first adsorption process to obtain first treated wastewater;

[0009] The first adsorption process is: first, the first wastewater is subjected to first adsorption pretreatment using a tubular ceramic membrane adsorption, and then subjected to first adsorption treatment using modified carbon ball adsorption and tubular ultrafiltration membrane adsorption;

[0010] Process 3, re-cooking agent recovery: the waste water generated by re-cooking and the waste water generated by secondary water washing are second waste water, the second waste water is treated by a second adsorption process based on modified carbon balls to obtain second treated waste water;

[0011] Process 4, waste water recycling: the waste water generated by the pre-washing section is treated by a microbial degradation membrane separation coupling process and is returned to the pre-washing section; the first treated waste water and the second treated waste water are returned to the pre-washing section after being supplemented with water and agents.

[0012] Further, the following technical constraints are made in the pre-washing, cooking and bleaching, re-cooking and pickling process sections in the traditional process:

[0013] Constraint 1, in the pre-washing process:

[0014] The additives include: LAS (sodium dodecyl benzene sulfonate) as a refining agent, the addition amount is 0.3% owf; EDTA (ethylenediamine tetraacetic acid) as a complexing agent, the addition amount is 0.3% owf; JFC (fatty alcohol polyoxyethylene ether) as a penetrating agent, the addition amount is 0.3% owf; sodium polyacrylate as a dispersing agent, the addition amount is 0.3% owf;

[0015] Note: The % owf addition amount unit used here refers to the ratio of the weight of the additive to the weight of the gray fabric;

[0016] The process parameters are: the temperature is 80-85℃, and the time is 30-40min;

[0017] Constraint 2, in the cooking and bleaching process:

[0018] The additives include: LAS as a refining agent, the addition amount is 1.2% owf; EDTA as a complexing agent, the addition amount is 1.2% owf; NaOH with a mass fraction of 98%, the addition amount is 1-1.5% owf; H2O2 with a mass fraction of 27.5%, the addition amount is 8% owf;

[0019] The process parameters are: the temperature is 98-100℃, and the time is 60-70min;

[0020] Constraint 3, in the re-cooking process:

[0021] The additives include: EDTA as a complexing agent, the addition amount is 1.2% owf; NaOH with a mass fraction of 98%, the addition amount is 1-1.5% owf; H2O2 with a mass fraction of 27.5%, the addition amount is 8% owf;

[0022] The process parameters are: the temperature is 98-100℃, and the time is 60-70min;

[0023] Constraint 4, in the pickling process:

[0024] The additive is H2SO4, and the amount of the additive is determined according to the amount of the additive when the pH value of the water in the pickling process section is neutral.

[0025] Description: The refining agent LAS is used to remove natural impurities (such as oil, wax) in the gray cloth and dirt introduced in the process; the chelating agent EDTA is often used in high-alkaline and high-temperature bleaching processes, and is used to chelate metal ions (such as calcium, magnesium, iron, etc.) in water to prevent them from reacting with other agents; the penetrating agent JFC is used to improve the permeability of the agent, so that the agent can act more uniformly on the inside of the fiber; the dispersant sodium polyacrylate can prevent dirt and impurities from redepositing on the fiber, and has excellent dispersing ability.

[0026] Further, in the first adsorption process of process 2, the solid-liquid ratio of the modified carbon spheres added in the first wastewater is 40-45 g / L, the adsorption temperature is 25-30℃, and the adsorption time is 10-12 h;

[0027] In the second adsorption process of process 3, the solid-liquid ratio of the modified carbon spheres added in the second wastewater is 30-34 g / L, the adsorption temperature is 25-30℃, and the adsorption time is 5-6 h.

[0028] Further, the surface of the modified carbon spheres in process 2 and process 3 is enriched with cationic groups and basic groups, and the iodine value is in the range of 1300-1330 iodine, and the arlan value is in the range of 20-25 arlan, and the preparation steps are as follows:

[0029] SA-1, a solid product one prepared as a carbon sphere precursor based on a template method;

[0030] SA-2, carbonization and etching: the solid product one prepared in SA-1 is carbonized by gradient heating under a protective atmosphere, and then the product is immersed in 20% HF for etching for 48 h, and finally dried to obtain a solid powder two; the parameters of the gradient heating are as follows: based on room temperature, the temperature is increased to 320℃ at a rate of 3-5℃ and kept for 1.3-1.5 h, and then the temperature is increased to 850-870℃ at a rate of 5-7℃ and kept for 2-2.5 h;

[0031] SA-3, pore-forming activation: the solid powder two prepared in SA-2 is mixed with KOH, calcined at 800℃ for 2 h under a protective atmosphere to obtain modified carbon spheres with surface depressions in the form of bowls; let n be a rate coefficient and n∈R + , then the amount of the solid powder two added is 1 g, and the amount of KOH added is n[5,7] mL.

[0032] Description: 3-aminophenol can be solubilized into the hydrophobic inner core of the double-tetradecyl dimethyl ammonium bromide micelles. When ammonia water and formaldehyde are added, 3-aminophenol and formaldehyde can undergo condensation reaction at the interface of double-tetradecyl dimethyl ammonium bromide. Ammonia water can make a large amount of hydroxymethyl substitutes in the mixed solution of water and ethanol. When the silicate anions hydrolyzed from TEOS meet the positively charged double-tetradecyl dimethyl ammonium bromide, strong electrostatic force makes them form a unique open-bowl-shaped soft template structure, and finally the modified carbon spheres with open-bowl-shaped structure are prepared by carbonization.

[0033] Further, the step of the solid product one prepared based on the template method in SA-1 is:

[0034] SA-1-1, first, deionized water and anhydrous ethanol are added to the reactor, and stirring is continued at 40℃, 300-350r / min, and then 3-aminophenol, double-tetradecyl dimethyl ammonium bromide, ammonia solution, formaldehyde solution and TEOS are sequentially added based on a time interval of 15-25min to obtain system one;

[0035] Let n be the rate coefficient and n∈R + , then the amount of deionized water added is 40mL, the amount of anhydrous ethanol added is n[40, 50]mL, the amount of 3-aminophenol added is n[0.5, 0.7]g, the amount of double-tetradecyl dimethyl ammonium bromide added is n[0.5, 1.2]g, the amount of ammonia solution with a concentration of 25wt.% added is n[0.5, 0.8]mL, the amount of formaldehyde solution with a concentration of 40wt.% added is n[0.8, 1.2]mL, and the amount of TEOS added is n[2, 5]mL;

[0036] SA-1-2, the system one prepared in SA-1-1 is continuously stirred at 30℃, 300-350r / min for 24h, and then first drying, cooling, centrifugation, washing and second drying are performed to obtain a solid powder one.

[0037] Further, the modified carbon spheres prepared in SA-3 are subjected to magnetization treatment, the steps of which are as follows: the modified carbon spheres prepared in SA-3 are added to deionized water and continuously stirred, then Fe3O4 powder is added and subjected to hydrothermal treatment at 180-200℃ for 10-12h, and finally magnetically separated, washed and dried to obtain magnetized modified carbon spheres; the mass ratio of the modified carbon spheres to the Fe3O4 powder is 2-2.5:1.

[0038] Note: The main purpose of magnetization treatment is to make the modified carbon spheres magnetic, which facilitates their subsequent removal and desorption from wastewater. It should be noted that although magnetic modification can greatly improve the recovery rate of modified carbon spheres, the Fe3O4 particles occupy the concave bowl-shaped portion of the modified carbon spheres, which will lead to a decrease in the specific surface area of ​​the modified carbon spheres and weaken their adsorption performance. Therefore, in practical applications, it is necessary to reasonably select modified carbon spheres or magnetically modified carbon spheres according to the actual situation.

[0039] Furthermore, the preparation steps of the ultrafiltration membrane in the tubular ultrafiltration membrane in process 2 are:

[0040] SB-1, preparing casting solution;

[0041] Polyethylene glycol 300 and graphene oxide were added to hexafluoroisopropanol and ultrasonically stirred for 2-3 hours; then PSf polymer particles were added under continuous stirring for 15-20 minutes; then, the mixture was heated at 60-65°C with continuous stirring until the material was melted and evenly distributed, and finally, bubbles were expelled under a negative pressure of 120-130 Pa and a temperature of 30-33°C to obtain a casting solution;

[0042] Let n be the multiplication coefficient and n∈R + , the amount of PSf polymer particles added is 20 g, the amount of polyethylene glycol 300 added is n[20,30] mL, the amount of graphene oxide added is n[0.5,0.8] g, and the amount of hexafluoroisopropanol added is n[100,110] mL;

[0043] SB-2. Ultrafiltration membrane was prepared by scraping method: the scraper speed was 4-5 m / s, the scraper height was 100 μm, and the prepared ultrafiltration membrane was stored in 0.5% NaHSO 3 solution after washing.

[0044] Description: The present invention uses graphene oxide as a filler to improve the pore structure of the membrane, adjust the pore size and membrane pore morphology of the membrane substrate, generate long strip-shaped pores that penetrate the membrane matrix, and improve the water flux of the membrane; not only that, due to the change in membrane pore morphology, the mechanical strength of the membrane is also improved.

[0045] Furthermore, the concentration process specifically uses an evaporative crystallizer to remove sulfate from the wastewater by evaporative crystallization.

[0046] Furthermore, the specific steps of the microbial degradation membrane separation coupling process are: adjusting and balancing the pH value, temperature and turbidity of the wastewater generated in the pre-wash section, discharging it into the microbial treatment pool after adjustment to use microorganisms to degrade organic matter in the wastewater, using biofilm to perform deep separation of organic matter, heavy metal ions and trace pollutants after biological treatment, and finally performing ozone sterilization. The water after ozone sterilization is returned to the pre-wash section for reuse, ensuring the quality of pre-washing while reducing water demand.

[0047] Compared with the existing grey cloth deperming wastewater treatment method, the beneficial effects of the present application are:

[0048] (1) The present application realizes grey cloth deperming agent resource recovery and zero discharge of wastewater by segmented treatment and resource recovery and reuse. Compared with the traditional grey cloth deperming wastewater treatment process which mixes all process segment wastewater for treatment, the present application realizes resource recovery of agents by selectively removing interference factors in selected process segments, effectively reduces the complexity of wastewater, significantly reduces the wastewater treatment cost, and effectively reduces energy loss through heat recovery.

[0049] (2) The present application also designs modified carbon spheres and ultrafiltration membranes for adsorption treatment according to the pollutant characteristics of grey cloth deperming wastewater. The modified carbon spheres designed by the present application have an open bowl structure, so as to significantly increase the surface area and mesopore rate, and provide attachment sites and structural support for subsequent magnetic modification. Furthermore, the ultrafiltration membrane designed by the present application improves the shape and permeability of the membrane pores, and improves the water flux and mechanical strength of the ultrafiltration membrane. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 is the process flow chart of the present application. DETAILED DESCRIPTION

[0051] In order to further illustrate the manner of carrying out the present application and the effects achieved, the technical solutions of the present application will be described in detail below in conjunction with experiments.

[0052] Example 1: The content described in this example is a grey cloth deperming wastewater zero discharge treatment method, which aims to improve the traditional process:

[0053] 1. In the pre-washing, boiling and bleaching, re-boiling and pickling process segments in the traditional process, the following technical constraints are made:

[0054] Constraint 1, in the pre-washing process:

[0055] The additives include: LAS as a refining agent, the addition amount is 0.3% owf; EDTA as a complexing agent, the addition amount is 0.3% owf; JFC as a penetrating agent, the addition amount is 0.3% owf; sodium polyacrylate as a dispersing agent, the addition amount is 0.3% owf;

[0056] The process parameters are: temperature is 80℃, time is 30min;

[0057] Constraint 2, in the boiling and bleaching process:

[0058] The additives include: LAS as a refining agent, the addition amount is 1.2% owf; EDTA as a complexing agent, the addition amount is 1.2% owf; NaOH with a mass fraction of 98%, the addition amount is 1% owf; H2O2 with a mass fraction of 27.5%, the addition amount is 8% owf;

[0059] The process parameters are: the temperature is 98℃, and the time is 60min;

[0060] Constraint 3, in the re-cooking process:

[0061] The additives include: EDTA as a complexing agent, the addition amount is 1.2% owf; NaOH with a mass fraction of 98%, the addition amount is 1% owf; H2O2 with a mass fraction of 27.5%, the addition amount is 8% owf;

[0062] The process parameters are: the temperature is 98℃, and the time is 60min;

[0063] Constraint 4, in the pickling process:

[0064] The additive is H2SO4, and the addition amount is the addition amount when the pH value of the water in the pickling process section is neutral.

[0065] Constraint 5, in the concentration process, an evaporation crystallizer is used for evaporation crystallization to remove sulfates in the wastewater.

[0066] 2, the technical improvements made to each process section are:

[0067] Process 1, waste heat recovery: a heat exchange process is set in the boiling and bleaching and re-cooking process sections to recover waste heat, and then the waste heat is transmitted to the concentration process section;

[0068] Process 2, boiling and bleaching agent recovery: the wastewater generated by boiling and bleaching and the wastewater generated by the first water washing are referred to as first wastewater, and the first wastewater is treated based on a first adsorption process to obtain first treated wastewater;

[0069] The first adsorption process is: first, a tubular ceramic membrane adsorption is used for first adsorption pretreatment of the first wastewater, and then a modified carbon ball adsorption and a tubular ultrafiltration membrane adsorption are used for first adsorption treatment;

[0070] Process 3, re-cooking agent recovery: the wastewater generated by re-cooking and the wastewater generated by the second water washing are referred to as second wastewater, and the second wastewater is treated using a second adsorption process based on a modified carbon ball to obtain second treated wastewater;

[0071] Process 4, wastewater reuse: the wastewater generated in the pre-washing section is treated based on a microbial degradation membrane separation coupling process and is returned to the pre-washing section; the first treated wastewater and the second treated wastewater are returned to the pre-washing section after being supplemented with water and agents.

[0072] The first adsorption process is: first, the first wastewater is pretreated by using a tubular ceramic membrane adsorption, and then the first adsorption treatment is performed by using modified carbon ball adsorption and tubular ultrafiltration membrane adsorption;

[0073] In the first adsorption process, the solid-liquid ratio of the modified carbon balls added in the first wastewater is 40 g / L, the adsorption temperature is 25 DEG C, and the adsorption time is 10 h;

[0074] In the second adsorption process, the solid-liquid ratio of the modified carbon balls added in the second wastewater is 30 g / L, the adsorption temperature is 25 DEG C, and the adsorption time is 5 h;

[0075] In the microbial degradation membrane separation coupling process, the specific steps of the microbial degradation membrane separation coupling process are:

[0076] The pH value, temperature and turbidity of the wastewater generated in the pre-washing section are adjusted and balanced, and after adjustment, they are discharged into the microbial treatment tank to degrade the organic matter in the wastewater by using microorganisms, and after biological treatment, the biological membrane is used for deep separation of organic matter, heavy metal ions and trace pollutants, and finally ozone sterilization is performed, and the water after ozone sterilization is returned to the pre-washing section for reuse, thereby ensuring the pre-washing quality while reducing water demand.

[0077] 3. The preparation steps of the modified carbon balls are:

[0078] SA-1, preparing a carbon ball precursor based on a template method;

[0079] SA-1-1, first, deionized water and anhydrous ethanol are added to a reactor, and stirring is continuously performed at 40 DEG C and 300 r / min, and then based on a time interval of 15 min, 3-aminophenol, ditetradecyl dimethyl ammonium bromide, an ammonia solution, a formaldehyde solution and TEOS are sequentially added to obtain a system one;

[0080] The addition amount of the deionized water is 40 mL, the addition amount of the anhydrous ethanol is 40 mL, the addition amount of the 3-aminophenol is 0.5 g, the addition amount of the ditetradecyl dimethyl ammonium bromide is 0.5 g, the addition amount of the ammonia solution with a concentration of 25 wt.% is 0.5 mL, the addition amount of the formaldehyde solution with a concentration of 40 wt.% is 0.8 mL, and the addition amount of the TEOS is 2 mL;

[0081] SA-1-2, the system one prepared in SA-1-1 is continuously stirred at 30 DEG C and 300 r / min for 24 h, and then a solid powder one is obtained by first drying, cooling, centrifugation, washing and second drying;

[0082] SA-2, carbonization and etching;

[0083] The solid product prepared in SA-1 is carbonized by gradient heating, and then the product is etched in 20% HF for 48 h, and finally dried to obtain a solid powder II;

[0084] The gradient heating parameters are: based on room temperature, the temperature is increased to 320℃ at a rate of 3℃ and kept for 1.3 h, and then increased to 850℃ at a rate of 5℃ and kept for 2 h;

[0085] SA-3, pore-forming activation;

[0086] The solid powder II prepared in SA-2 is mixed with KOH, calcined at 800℃ for 2 h under a protective atmosphere to obtain modified carbon spheres with surface depressions in the form of bowls; the addition amount of the solid powder II is 1 g, and the addition amount of KOH is 5 mL.

[0087] 4. The preparation steps of the ultrafiltration membrane in the tubular ultrafiltration membrane are:

[0088] SB-1, preparation of casting solution;

[0089] Polyethylene glycol 300 and graphene oxide are added to hexafluoroisopropanol, and ultrasonic stirring is performed for 2 h; then PSf polymer particles are added under continuous stirring for 15 min; then continuous stirring is performed under heating at 60℃ until the material is melted and uniformly distributed, and finally the bubbles are discharged under a negative pressure of 120 Pa and at 30℃ to obtain the casting solution;

[0090] The addition amount of PSf polymer particles is 20 g, the addition amount of polyethylene glycol 300 is 20 mL, the addition amount of graphene oxide is 0.5 g, and the addition amount of hexafluoroisopropanol is 100 mL;

[0091] SB-2, preparation of ultrafiltration membrane using the blade casting method: the scraper speed is 4 m / s, and the scraper height is 100 μm; the prepared ultrafiltration membrane is washed and stored in a 0.5% NaHSO3 solution.

[0092] Example 2: This example is based on the scheme designed in Example 1, and is intended to illustrate the scheme under another parameter.

[0093] 1. In the pre-washing, boiling and bleaching, re-boiling and pickling process sections in the traditional process, the following technical constraints are made:

[0094] Constraint 1, in the pre-washing process:

[0095] The additives include: LAS as a refining agent, the addition amount is 0.3% owf; EDTA as a complexing agent, the addition amount is 0.3% owf; JFC as a penetrating agent, the addition amount is 0.3% owf; sodium polyacrylate as a dispersing agent, the addition amount is 0.3% owf;

[0096] Process parameters: temperature 85℃, time 40min;

[0097] Constraint 2, in the boiling and bleaching process:

[0098] Additives include: LAS as a refining agent, the addition amount is 1.2%owf; EDTA as a complexing agent, the addition amount is 1.2%owf; mass fraction of 98% NaOH, the addition amount is 1.5%owf; mass fraction of 27.5% H2O2, the addition amount is 8%owf;

[0099] Process parameters: temperature 100℃, time 70min;

[0100] Constraint 3, in the reboiling process:

[0101] Additives include: EDTA as a complexing agent, the addition amount is 1.2%owf; mass fraction of 98% NaOH, the addition amount is 1.5%owf; mass fraction of 27.5% H2O2, the addition amount is 8%owf;

[0102] Process parameters: temperature 100℃, time 70min;

[0103] Constraint 4, in the pickling process:

[0104] Additives: H2SO4, the addition amount is the addition amount when the pH value of the water in the pickling process section is neutral.

[0105] Constraint 5, in the concentration process, evaporation crystallization is used to remove sulfates in wastewater.

[0106] 2, the technical improvements made to each process section are:

[0107] Process 1, waste heat recovery: set up a heat exchange process in the boiling and bleaching and reboiling process sections to recover waste heat, which is then transmitted to the concentration process section;

[0108] Process 2, boiling agent recovery: the wastewater produced by boiling and the wastewater produced by the first water washing is called first wastewater, which is treated based on the first adsorption process to obtain first treated wastewater;

[0109] The first adsorption process is: first, use a tubular ceramic membrane adsorption to do a first adsorption pretreatment on the first wastewater, then use a modified carbon ball adsorption and a tubular ultrafiltration membrane adsorption to do a first adsorption treatment;

[0110] Process 3, reboiling agent recovery: the wastewater produced by reboiling and the wastewater produced by the second water washing is called second wastewater, which is treated using a second adsorption process based on modified carbon balls to obtain second treated wastewater;

[0111] Process 4, wastewater reuse: the wastewater generated in the pre-washing section is treated by a microbial degradation membrane separation coupling process and is returned to the pre-washing section; the first treated wastewater and the second treated wastewater are returned to the pre-washing section after being supplemented with water and chemicals.

[0112] The first adsorption process is: first, the first wastewater is pretreated by using a tubular ceramic membrane adsorption, and then the first wastewater is treated by using modified carbon sphere adsorption and tubular ultrafiltration membrane adsorption;

[0113] In the first adsorption process, the solid-liquid ratio of the modified carbon spheres added to the first wastewater is 40 g / L, the adsorption temperature is 25°C, and the adsorption time is 10 h;

[0114] In the second adsorption process, the solid-liquid ratio of the modified carbon spheres added to the second wastewater is 30 g / L, the adsorption temperature is 25°C, and the adsorption time is 5 h;

[0115] In the microbial degradation membrane separation coupling process, the specific steps of the microbial degradation membrane separation coupling process are:

[0116] The pH value, temperature and turbidity of the wastewater generated in the pre-washing section are adjusted and balanced, and after adjustment, the wastewater is discharged into a microbial treatment tank to degrade organic matter in the wastewater by using microorganisms. After biological treatment, the organic matter, heavy metal ions and trace pollutants are separated by using a biological membrane, and finally, ozone sterilization is performed. The water after ozone sterilization is returned to the pre-washing section for reuse, thereby ensuring the quality of pre-washing and reducing water demand.

[0117] 3. The preparation steps of the modified carbon spheres are:

[0118] SA-1, preparation of carbon sphere precursors based on a template method;

[0119] SA-1-1, first, deionized water and anhydrous ethanol are added to a reactor, and stirring is continuously performed at 40°C and 350 r / min, and then 3-aminophenol, ditetradecyl dimethyl ammonium bromide, an ammonia solution, a formaldehyde solution and TEOS are sequentially added based on a time interval of 25 min to obtain system one;

[0120] The addition amount of deionized water is 40 mL, the addition amount of anhydrous ethanol is 50 mL, the addition amount of 3-aminophenol is 0.5 g, the addition amount of ditetradecyl dimethyl ammonium bromide is 1.2 g, the addition amount of the ammonia solution with a concentration of 25 wt.% is 0.8 mL, the addition amount of the formaldehyde solution with a concentration of 40 wt.% is 1.2 mL, and the addition amount of TEOS is 5 mL;

[0121] SA-1-2, the system one prepared in S2-1-1 is continuously stirred at 30°C and 350 r / min for 24 h, and then solid powder one is obtained by first drying, cooling, centrifugation, washing and second drying.

[0122] SA-2, carbonization and etching;

[0123] The solid product prepared in SA-1 was carbonized by gradient heating under a protective atmosphere, and then the product was immersed in 20% HF for etching for 48 h, and finally dried to obtain a solid powder II.

[0124] The parameters of gradient heating were as follows: based on room temperature, the temperature was increased to 320℃ at a rate of 5℃ and kept for 1.5 h, and then increased to 870℃ at a rate of 7℃ and kept for 2.5 h;

[0125] SA-3, pore-forming activation;

[0126] The solid powder II prepared in SA-2 was mixed with KOH, and calcined at 800℃ for 2 h under a protective atmosphere to obtain modified carbon spheres with surface depressions in the form of bowls; the addition amount of the solid powder II was 1 g, and the addition amount of KOH was 7 mL.

[0127] 4. The preparation steps of the ultrafiltration membrane in the tubular ultrafiltration membrane are as follows:

[0128] SB-1, preparation of casting solution;

[0129] Polyethylene glycol 300 and graphene oxide were added to hexafluoroisopropanol and ultrasonically stirred for 3 h; then PSf polymer particles were added under continuous stirring for 20 min; then the material was heated under continuous stirring at 65℃ until it melted and was uniformly distributed; finally, the bubbles were discharged under a negative pressure of 130 Pa and a temperature of 33℃ to obtain the casting solution.

[0130] The addition amount of PSf polymer particles was 20 g, the addition amount of polyethylene glycol 300 was 30 mL, the addition amount of graphene oxide was 0.8 g, and the addition amount of hexafluoroisopropanol was 110 mL.

[0131] SB-2, preparation of ultrafiltration membrane using the blade casting method: the scraper speed was 5 m / s, and the scraper height was 100 μm; the prepared ultrafiltration membrane was washed and stored in a 0.5% NaHSO3 solution.

[0132] Example 3: This example is based on the scheme designed in Example 1, and aims to illustrate a low-energy and carbon-reduced gray fabric desizing and scouring wastewater treatment method under another design. Except for the following content, the rest is the same as Example 1:

[0133] The modified carbon spheres prepared in SA-3 were magnetized, and the steps were as follows: 20 g of the modified carbon spheres prepared in SA-3 were added to 50 mL of deionized water and continuously stirred, then 10 g of Fe3O4 powder was added and hydrothermally treated at 200℃ for 12 h, and finally the magnetized modified carbon spheres were obtained after magnetic separation, washing and drying.

[0134] Experimental Example 1: The purpose of this experimental example is to compare the performance of the modified carbon sphere camera designed in the application with different types of activated carbon.

[0135] The wastewater sample used in this experimental example contains 100 mL, with a COD concentration of 13000 mg / L, a phenol concentration of 610 mg / L, and a color of 13 times.

[0136] Since iodine value and lan value are important indicators affecting the adsorption performance of activated carbon, higher lan value is beneficial to the adsorption and removal of COD and phenol by activated carbon, so the following control experiment is designed:

[0137] Table 1 Comparison of iodine values of different types of activated carbon

[0138]

[0139] Table 2 Comparison of lan values of different types of activated carbon

[0140]

[0141] From the data in Tables 1 and 2, it can be seen that the modified carbon sphere designed in the application has a higher iodine value and lan value than the traditional activated carbon due to the presence of a large number of cationic groups and basic groups on the surface, which removes anionic groups and acidic groups, and the mesoporous structure is developed. Therefore, the adsorption and removal effect of the modified carbon sphere designed in the application on COD and phenol is excellent (there is a certain positive correlation between wastewater color and phenol concentration;).

[0142] Experimental Example 2: This experimental example designs a complex bleaching experiment based on the scheme in Example 1, the contents are as follows:

[0143] Table 3 Complex bleaching experiment

[0144]

[0145] From the data in Table 3, compared with the traditional wastewater treatment which discharges and treats wastewater from each process section with high energy consumption and high difficulty, the segmented treatment and reuse to the process section form proposed by this method has the following advantages in wastewater treatment and resource utilization under the principle of entropy:

[0146] The traditional centralized processing mode often needs a large amount of energy to process highly mixed wastewater, which not only has high energy consumption, but also has high system entropy increase due to the complexity of different components in the wastewater. The present application reduces the complexity of wastewater mixing by segmenting the processing and recycling the wastewater, combined with waste heat recovery and selective removal of key pollutants, to achieve a more efficient and environmentally friendly wastewater treatment and resource utilization method (such as separately processing wastewater with high pectin and high COD, which can more effectively remove specific pollutants, reduce unnecessary energy consumption, and reduce system entropy increase); by processing wastewater in each process section separately, the direction of pollutants can be better controlled, avoiding the spread of pollutants in the entire system (such as recycling low-pectin and low-color wastewater to the pre-washing section, which not only reduces the use of fresh water and some chemicals, but also effectively controls the recycling of pollutants, which helps to reduce the system entropy increase); in the traditional centralized processing mode, a large amount of energy is lost during the long-time and long-distance transmission of wastewater, while the present application does not have this problem.

Claims

1. A grey fabric decontamination wastewater zero discharge treatment method, the steps are: the grey fabric is sequentially through pre-washing, boiling and bleaching, one water washing, re-boiling, secondary water washing, pickling, and concentration process for degreasing and bleaching, characterized in that, In The above process is added with the following process section: Process 1, waste heat recovery: a heat exchange process is arranged in the boiling and bleaching and re-boiling process section to recover waste heat, and then the waste heat is transmitted to the concentration process section; Process 2, boiling and bleaching agent recovery: the waste water generated by the boiling and the waste water generated by the first water washing is referred to as first waste water, the first waste water is treated based on a first adsorption process to obtain first treated waste water; The first adsorption process is: first, a first adsorption pretreatment is performed on the first waste water using a tubular ceramic membrane adsorption, and then a first adsorption treatment is performed using modified carbon sphere adsorption and tubular ultrafiltration membrane adsorption; Process 3, re-boiling agent recovery: the waste water generated by the re-boiling and the waste water generated by the second water washing is referred to as second waste water, the second waste water is treated using a second adsorption process based on modified carbon spheres to obtain second treated waste water; Process 4, waste water recycling: the waste water generated in the pre-washing section is treated based on a microbial degradation membrane separation coupling process and is returned to the pre-washing section; The first treated waste water and the second treated waste water are returned to the pre-washing section after being supplemented with water and agents; The surface of the modified carbon spheres in the process 2 and the process 3 is enriched with cationic groups and basic groups, and the iodine value is in the range of 1300-1330 iodine, and the arlan value is in the range of 20-25 arlan; the preparation method of the modified carbon spheres is: SA-1, a solid product one is prepared as a carbon sphere precursor based on a template method; SA-1-1, first, deionized water and anhydrous ethanol are added to a reactor, stirring is continuously performed at 40°C and 300-350 r / min, then 3-aminophenol, ditetradecyl dimethyl ammonium bromide, ammonia solution, formaldehyde solution and TEOS are sequentially added based on a time interval of 15-25 min to obtain system one; Let n be a scale factor and The amount of deionized water added is 40 mL, the amount of anhydrous ethanol added is [40n, 50n] mL, the amount of 3-aminophenol added is [0.5n, 0.7n] g, the amount of cetrimonium bromide added is [0.5n, 1.2n] g, the amount of ammonia solution with a concentration of 25 wt% added is [0.5n, 0.8n] mL, the amount of formaldehyde solution with a concentration of 40 wt% added is [0.8n, 1.2n] mL, and the amount of TEOS added is [2n, 5n] mL. SA-1-2, system one prepared in SA-1-1 is continuously stirred at 30°C and 300-350 r / min for 24h, then solid powder one is obtained through first drying, cooling, centrifugation, washing and second drying; SA-2, carbonization and etching: the solid product one prepared in SA-1 is carbonized through gradient heating under a protective atmosphere, then the product is immersed in 20%HF for etching for 48h, and finally solid powder two is obtained through drying; the parameters of the gradient heating are: based on room temperature, the temperature is increased to 320°C at a rate of 3-5°C and is kept for 1.3-1.5h, then the temperature is increased to 850-870°C at a rate of 5-7°C and is kept for 2-2.5h; SA-3, pore-forming activation: solid powder two prepared in SA-2 is mixed with KOH, calcination is performed at 800°C for 2h under a protective atmosphere to obtain modified carbon spheres with surface depressions in the form of bowls; Let n be the multiplication factor and The amount of the solid powder II to be added is 1 g, and the amount of KOH to be added is [5n, 7n] mL.

2. A greige goods deperming effluent zero discharge treatment method according to claim 1, characterized by, The following technical constraints are made for the pre-washing, boiling and bleaching, re-boiling and pickling process sections: Constraint 1, in the pre-washing process: The additives include: LAS as a refining agent, the addition amount is 0.3%owf; EDTA as a complexing agent, the addition amount is 0.3%owf; JFC as a penetrating agent, the addition amount is 0.3%owf; sodium polyacrylate as a dispersing agent, the addition amount is 0.3%owf; The process parameters are: the temperature is 80-85°C, and the time is 30-40 min; Constraint 2, in the boiling and bleaching process: The additives include: LAS as a refining agent, the addition amount is 1.2%owf; EDTA as a complexing agent, the addition amount is 1.2%owf; 98% NaOH, the addition amount is 1~1.5%owf; 27.5% H2O2, the addition amount is 8%owf; The process parameters are: the temperature is 98~100℃, the time is 60~70 min; Constraint 3, in the reboiling process: The additives include: EDTA as a complexing agent, the addition amount is 1.2%owf; 98% NaOH, the addition amount is 1~1.5%owf; 27.5% H2O2, the addition amount is 8%owf; The process parameters are: the temperature is 98~100℃, the time is 60~70 min; Constraint 4, in the pickling process: The additive is H2SO4, and the addition amount is the addition amount when the pH value of the water in the pickling process section is neutral.

3. A greige goods deperming effluent zero discharge treatment method according to claim 1, characterized by, In the first adsorption process of the process 2, the solid-liquid ratio of the modified carbon balls added in the first wastewater is 40~45 g / L, the adsorption temperature is 25~30℃, and the adsorption time is 10~12 h; In the second adsorption process of the process 3, the solid-liquid ratio of the modified carbon balls added in the second wastewater is 30~34 g / L, the adsorption temperature is 25~30℃, and the adsorption time is 5~6 h.

4. A greige goods deperming effluent zero discharge treatment method according to claim 1, characterized by, The preparation steps of the ultrafiltration membrane in the process 2 are: SB-1, preparing the casting solution: polyethylene glycol 300 and graphene oxide are added to hexafluoroisopropanol, and ultrasonic stirring is performed for 2~3 h; then PSf polymer particles are added under continuous stirring for 15~20 min; then the material is heated under continuous stirring at 60~65℃ until it is melted and uniformly distributed, and finally the bubbles are discharged under a negative pressure of 120~130 Pa and a temperature of 30~33℃, to obtain the casting solution; Let n be the scale factor and The PSf polymer particles are added in an amount of 20 g, the polyethylene glycol 300 is added in an amount of [20n, 30n] mL, the graphene oxide is added in an amount of [0.5n, 0.8n] g, and the hexafluoroisopropanol is added in an amount of [100n, 110n] mL. SB-2, preparing the ultrafiltration membrane by using the blade coating method: the scraper speed is 4~5 m / s, and the scraper height is 100 μm; the prepared ultrafiltration membrane is washed and stored in a 0.5% NaHSO3 solution.

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